US20060147402A1 - Composition comprising a sequenced polymer and a gelling agent - Google Patents
Composition comprising a sequenced polymer and a gelling agent Download PDFInfo
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- US20060147402A1 US20060147402A1 US10/528,835 US52883503A US2006147402A1 US 20060147402 A1 US20060147402 A1 US 20060147402A1 US 52883503 A US52883503 A US 52883503A US 2006147402 A1 US2006147402 A1 US 2006147402A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/26—Aluminium; Compounds thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/8105—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- A61K8/8111—Homopolymers or copolymers of aliphatic olefines, e.g. polyethylene, polyisobutene; Compositions of derivatives of such polymers
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- A61K8/8152—Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/817—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions or derivatives of such polymers, e.g. vinylimidazol, vinylcaprolactame, allylamines (Polyquaternium 6)
- A61K8/8182—Copolymers of vinyl-pyrrolidones. Compositions of derivatives of such polymers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/89—Polysiloxanes
- A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/90—Block copolymers
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/92—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof
- A61K8/922—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof of vegetable origin
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/92—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof
- A61K8/927—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof of insects, e.g. shellac
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
- A61Q1/02—Preparations containing skin colorants, e.g. pigments
- A61Q1/04—Preparations containing skin colorants, e.g. pigments for lips
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
- A61Q1/02—Preparations containing skin colorants, e.g. pigments
- A61Q1/04—Preparations containing skin colorants, e.g. pigments for lips
- A61Q1/06—Lipsticks
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
- A61Q1/02—Preparations containing skin colorants, e.g. pigments
- A61Q1/10—Preparations containing skin colorants, e.g. pigments for eyes, e.g. eyeliner, mascara
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q3/00—Manicure or pedicure preparations
- A61Q3/02—Nail coatings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/59—Mixtures
- A61K2800/594—Mixtures of polymers
Definitions
- the present invention relates to a cosmetic composition for making up or caring for human bodily and facial skin, the scalp included, the lips or epidermal derivatives of human beings, such as the hair, eyebrows, eyelashes or nails, which comprises a particular block polymer.
- the composition may be a loose or compact powder, a foundation, a rouge, an eyeshadow, a concealer, a blusher, a lipstick, a lip balm, a lipgloss, a lip pencil, an eye pencil, a mascara, an eyeliner, a nail varnish or even a body makeup product or a skin colouring product.
- compositions exhibit poor staying power over time, particularly as regards the colour.
- This poor staying power is characterized by an alteration in colour (colour change, fading), generally as a result of interaction with the sebum and/or perspiration secreted by the skin, in the case of foundation and of rouge or eyeshadow, or of interaction with the saliva, in the case of lipsticks.
- This alteration obliges the user to apply fresh makeup at frequent intervals, which may constitute a loss of time.
- Non-transfer compositions for the lips and skin are compositions which have the advantage of forming a deposit which at least in part is not deposited on the supports with which they are brought into contact (glass, clothing, cigarette, fabrics).
- Non-transfer compositions are generally based on silicone resins and volatile silicone oils and, although exhibiting improved staying properties, have the drawback of leaving on the skin and lips, following evaporation of the volatile silicone oils, a film which over time becomes uncomfortable (giving sensations of drying and tightening), thereby distancing a certain number of women from this type of lipstick.
- Non-transfer compositions contain volatile oils in association with film-forming polymers, which may be soluble in the oils, so as to limit the transfer of colour.
- the introduction of these polymers in solution in volatile solvents has the disadvantage of leading to formulas which are sometimes of low viscosity, owing in particular to the use of oil of very low viscosity and, in particular, of volatile oils. This low rheology goes hand in hand with awkward and unattractive application, with the added factor that the drying due to the presence of the volatiles may fix these inhomogeneities of deposition.
- composition of the invention may in particular constitute a product for making up the body, the lips or the epidermal derivatives of human beings which has, in particular, non-therapeutic treatment and/or care properties. It constitutes in particular a lipstick or a lipgloss, a rouge or eyeshadow, a tattooing product, a mascara, an eyeliner, a nail varnish, an artificial skin-tanning product or a hair colouring or haircare product.
- a composition comprising a cosmetically acceptable organic liquid medium, at least one particular block polymer and a gelling agent for the said medium exhibits good spreading and lubricity properties and allows a homogeneous makeup result to be obtained. Moreover, the composition is glossy, does not transfer and has good staying power.
- the invention provides first a cosmetic composition
- a cosmetic composition comprising, in a cosmetically acceptable organic liquid medium, at least one non-elastomeric film-forming ethylenic linear block polymer and a gelling agent for the said organic liquid medium.
- the present invention likewise provides a cosmetic composition
- a cosmetic composition comprising, in a cosmetically acceptable organic liquid medium, at least one film-forming ethylenic linear block polymer free from styrene units, and a gelling agent for the said organic liquid medium.
- the invention also relates to a method of making up the skin and/or the lips and/or the epidermal derivatives which consists in applying to the skin and/or the lips and/or the epidermal derivatives the composition as defined above.
- composition according to the invention may be applied to the skin of the face, the scalp and the body, the mucosae such as the lips, the inside of the lower eyelids, and the epidermal derivatives such as the nails, eyebrows, hair, eyelashes, and even body hair.
- composition according to the invention is not a rinse-off composition.
- the invention likewise relates to the cosmetic use of the composition defined above for enhancing the homogeneity of makeup on the skin and/or the lips and/or the epidermal derivatives.
- the invention provides finally for the use of a gelling agent in a composition comprising a block polymer as described above for the purpose of obtaining a composition which has good texture, is easy to apply and leads to a deposit which is glossy, does not migrate and/or has good staying power and/or is homogeneous.
- composition according to the present invention comprises at least one block polymer.
- block polymer is meant a polymer comprising at least 2 distinct blocks, preferably at least 3 distinct blocks.
- the block polymer of the composition according to the invention is an ethylenic polymer.
- ethylenic polymer is meant a polymer obtained by polymerizing monomers comprising an ethylenic unsaturation.
- the block polymer of the composition according to the invention is a linear polymer.
- a polymer having a non-linear structure is, for example, a polymer having a branched, starburst, graft or other structure.
- the block polymer of the composition according to the invention is a film-forming polymer.
- film-forming polymer is meant a polymer capable of forming, by itself or in the presence of an auxiliary film-forming agent, a continuous and adherent film on a support, particularly on keratin materials.
- the block polymer of the composition according to the invention is a non-elastomeric polymer.
- non-elastomeric polymer is meant a polymer which, when subjected to a stress intended to stretch it (for example by 30% relative to its initial length), does not return to a length substantially identical to its initial length when the stress ceases.
- non-elastomeric polymer denotes a polymer having an instantaneous recovery R i ⁇ 50% and a retarded recovery R 2h ⁇ 70% after having undergone 30% elongation.
- R i is ⁇ 30% and R2h is ⁇ 50%.
- a polymer film is prepared by pouring a solution of the polymer into a Teflon-coated mould and then drying it for 7 days in an environment controlled at 23 ⁇ 5° C. and 50 ⁇ 10% relative humidity.
- This sample is subjected to a tensile stress by means of an apparatus sold under the reference Zwick, under the same temperature and humidity conditions as for drying.
- the specimens are stretched at a speed of 50 mm/min, and the distance between the jaws is 50 mm, corresponding to the initial length (l 0 ) of the specimen.
- the instantaneous recovery Ri is determined as follows:
- the specimen is stretched by 30% ( ⁇ max ), i.e. about 0.3 times its initial length (l 0 );
- the stress is released by applying a return speed equal to the tensile speed, i.e. 50 mm/min, and the residual elongation of the specimen is measured as a percentage, after return to zero stress ( ⁇ i ).
- the residual elongation of the specimen is measured as a percentage ( ⁇ 2h ) 2 hours after return to zero stress.
- a polymer according to one embodiment of the invention possesses an instantaneous recovery R i of 10% and a retarded recovery R 2h of 30%.
- the block polymer of the composition according to the invention does not include a styrene unit.
- polymer free from styrene units is meant a polymer containing less than 10%, preferably less than 5%, preferably less than 2%, more preferably less than 1% by weight i) of styrene unit of formula —CH(C 6 H 5 )—CH 2 — or ii) of substituted styrene unit, for example methylstyrene, chlorostyrene or chloromethylstyrene.
- the block polymer of the composition according to the invention is obtained from aliphatic ethylenic monomers.
- aliphatic monomer is meant a monomer containing no aromatic group.
- the block polymer is an ethylenic polymer obtained from aliphatic ethylenic monomers comprising a carbon-carbon double bond and at least one ester group —COO— or amide group —CON—.
- the ester group may be bonded to one of the two unsaturated carbons via the carbon atom or the oxygen atom.
- the amide group may be bonded to one of the two unsaturated carbons via the carbon atom or the nitrogen atom.
- the block polymer comprises at least one first block and at least one second block.
- first and second blocks in no way condition the order of the said blocks (or sequences) in the structure of the polymer.
- the block polymer comprises at least one first block and at least one second block which have different glass transition temperatures (Tgs).
- first and second blocks may be connected to one another by an intermediate segment having a glass transition temperature between the glass transition temperatures of the first and second blocks.
- the block polymer comprises at least one first block and at least one second block connected to one another by an intermediate segment comprising at least one constituent monomer of the first block and at least one constituent monomer of the second block.
- the intermediate block is obtained essentially from constituent monomers of the first block and of the second block.
- the intermediate segment comprising at least one constituent monomer of the first block and at least one constituent monomer of the second block of the polymer is a random polymer.
- the block polymer comprises at least one first block and at least one second block which are incompatible in the organic liquid medium of the composition of the invention.
- blocks incompatible with one another is meant that the mixture formed from the polymer corresponding to the first block and from the polymer corresponding to the second block is not miscible in the liquid that is in a majority by weight in the organic liquid medium of the composition, at ambient temperature (25° C.) and atmospheric pressure (105 Pa), for a polymers mixture content greater than or equal to 5% by weight, relative to the total weight of the mixture (polymers and majority organic liquid), with the provisos that
- the said polymers are present in the mixture in an amount such that the respective weight ratio ranges from 10/90 to 90/10, and that
- each of the polymers corresponding to the first and second blocks has an average molecular mass (by weight or by number) equal to that of the block polymer ⁇ 15%.
- the organic liquid medium comprises a mixture of organic liquids
- the said polymers mixture is not miscible in at least one of them.
- the organic liquid medium comprises a single organic liquid
- the said liquid quite obviously, constitutes the liquid that is in a majority by weight.
- organic liquid medium is meant a medium comprising at least one organic liquid, in other words at least one organic compound which is liquid at ambient temperature (25° C.) and atmospheric pressure (10 5 Pa).
- the majority liquid of the organic liquid medium is a volatile or non-volatile oil (fat).
- the organic liquid is cosmetically acceptable (acceptable tolerance, toxicology and feel).
- the organic liquid medium is cosmetically acceptable in the sense that it is compatible with keratin materials, such as the oils or organic solvents commonly employed in cosmetic compositions.
- the majority liquid of the organic liquid medium is the polymerization solvent or one of the polymerization solvents of the block polymer, as are described below.
- polymerization solvent is meant a solvent or a mixture of solvents.
- the polymerization solvent may be selected in particular from ethyl acetate, butyl acetate, alcohols such as isopropanol and ethanol, aliphatic alkanes such as isododecane, and mixtures thereof.
- the polymerization solvent is a mixture of butyl acetate and isopropanol, or isododecane.
- the block polymer may be incorporated into the composition at a high solids content, typically more than 10%, more than 20% and more preferably more than 30% and more preferably still more than 45% by weight relative to the total weight of the composition, while being easy to formulate.
- the block polymer does not include silicon atoms in its skeleton.
- skeleton is meant the main chain of the polymer, as opposed to the pendent side chains.
- the polymer according to the invention is not water-soluble, which is to say that the polymer is not soluble in water or in a mixture of water and linear or branched lower monoalcohols having 2 to 5 carbon atoms, such as ethanol, isopropanol or n-propanol, without a change in pH, at an active substance content of at least 1% by weight, at ambient temperature (25° C.).
- the block polymer has a polydispersity index I of greater than 2.
- the block polymer used in the compositions according to the invention has a polydispersity index I of greater than 2, ranging for example from 2 to 9, preferably greater than or equal to 2.5, ranging for example from 2.5 to 8, and better still greater than or equal to 2.8, and in particular ranging from 2.8 to 6.
- the polydispersity index I of the polymer is equal to the ratio of the weight-average mass Mw to the number-average mass Mn.
- the weight-average (Mw) and number-average (Mn) molar masses are determined by liquid chromatography by gel permeation (THF solvent, calibration curve established with standards of linear polystyrene, refractometric detector).
- the weight-average mass (Mw) of the block polymer is preferably less than or equal to 300 000, and ranges for example from 35 000 to 200 000, better still from 45 000 to 150 000.
- the number-average mass (Mn) of the block polymer is preferably less than or equal to 70 000, and ranges for example from 10 000 to 60 000, better still from 12 000 to 50 000.
- Each block or sequence of the block polymer is obtained from one type of monomer or from two or more different types of monomers.
- each block may be composed of a homopolymer or of a copolymer; this copolymer, constituting the block, may in turn be random or alternating.
- ⁇ i being the mass fraction of the monomer i in the block in question and Tg i being the glass transition temperature of the homopolymer of the monomer i.
- Tgs indicated for the first and second blocks in the present specification are theoretical Tgs.
- the difference between the glass transition temperatures of the first and second blocks is generally greater than 10° C., preferably greater than 20° C. and more preferably greater than 30° C.
- the block polymer comprises at least one first block and at least one second block such that the first block may be selected from:
- the second block may be selected from a category a), b) or c) different from the first block.
- the expression “between . . . and . . . ” is intended to denote a range of values for which the limits mentioned are excluded, and the expression “from . . . to . . . and “ranging from . . . to . . . ” is intended to denote a range of values for which the limits are included.
- the block with a Tg of greater than or equal to 40° C. has, for example, a Tg ranging from 40 to 150° C., preferably greater than or equal to 50° C., ranging for example from 50° C. to 120° C., and better still greater than or equal to 60° C., ranging for example from 60° C. to 120° C.
- the block with a Tg of greater than or equal to 40° C. may be a homopolymer or a copolymer.
- the block with a Tg of greater than or equal to 40° C. may be obtained totally or partly from one or more monomers which are such that the homopolymer prepared from these monomers has a glass transition temperature of greater than or equal to 40° C.
- this block is a homopolymer, it is obtained from monomers which are such that the homopolymers prepared from these monomers have glass transition temperatures of greater than or equal to 40° C.
- This first block may be a homopolymer composed of a single type of monomer (for which the Tg of the corresponding homopolymer is greater than or equal to 40° C.).
- the first block is a copolymer
- it may be obtained totally or partly from one or more monomers, the nature and concentration of which are selected such that the Tg of the resulting copolymer is greater than or equal to 40° C.
- the copolymer may comprise, for example:
- Tgs of greater than or equal to 40° C., for example a Tg ranging from 40 to 150° C., preferably greater than or equal to 50° C., ranging for example from 50° C. to 120° C., and better still greater than or equal to 60° C., ranging for example from 60° C. to 120° C., and
- monomers which are such that the homopolymers prepared from these monomers have Tgs of less than 40° C., selected from monomers with a Tg of between 20 to 40° C. and/or monomers with a Tg of less than or equal to 20° C., for example a Tg ranging from ⁇ 100 to 20° C., preferably less than 15° C., especially ranging from ⁇ 80° C. to 15° C. and better still less than 10° C., for example ranging from ⁇ 50° C. to 0° C., as described later.
- the monomers whose homopolymers have a glass transition temperature of greater than or equal to 40° C. are selected, preferably, from the following monomers, also known as principal monomers:
- R 1 represents a linear or branched unsubstituted alkyl group containing from 1 to 4 carbon atoms, such as a methyl, ethyl, propyl or isobutyl group, or R 1 represents a C 4 to C 12 cycloalkyl group;
- R 7 and R 8 which are identical or different, each represent a hydrogen atom or a linear or branched C 1 to C 12 alkyl group, such as an n-butyl, t-butyl, isopropyl, isohexyl, isooctyl or isononyl group; or R 7 represents H and R 8 represents a 1,1-dimethyl-3-oxobutyl group and R′ denotes H or methyl.
- monomers that may be mentioned include N-butylacrylamide, N-t-butylacrylamide, N-isopropylacrylamide, N,N-dimethylacrylamide and N,N-dibutylacrylamide;
- Principal monomers that are particularly preferred are methyl methacrylate, isobutyl (meth)acrylate and isobornyl (meth)acrylate, and mixtures thereof.
- the block with a Tg of less than or equal to 20° C. has, for example, a Tg ranging from ⁇ 100 to 20° C., preferably less than or equal to 15° C., especially ranging from ⁇ 80° C. to 15° C. and better still less than or equal to 10° C., for example ranging from ⁇ 50° C. to 0° C.
- the block with a Tg of less than or equal to 20° C. may be a homopolymer or a copolymer.
- the block with a Tg of less than or equal to 20° C. may be obtained totally or partly from one or more monomers which are such that the homopolymer prepared from these monomers has a glass transition temperature of less than or equal to 20° C.
- this block is a homopolymer, it is obtained from monomers which are such that the homopolymers prepared from these monomers have glass transition temperatures of less than or equal to 20° C.
- This second block may be a homopolymer composed of a single type of monomer (for which the Tg of the corresponding homopolymer is less than or equal to 20° C.)
- the block with a Tg of less than or equal to 20° C. is a copolymer
- it may be obtained totally or partly from one or more monomers, the nature and concentration of which are selected such that the Tg of the resulting copolymer is less than or equal to 20° C.
- It may comprise, for example
- one or more monomers whose corresponding homopolymer has a Tg of less than or equal to 20° C. for example a Tg ranging from ⁇ 100° C. to 20° C., preferably less than 15° C., especially ranging from ⁇ 80° C. to 15° C. and better still less than 10° C., for example ranging from ⁇ 50° C. to 0° C., and
- one or more monomers whose corresponding homopolymer has a Tg of greater than 20° C. such as monomers with a Tg of greater than or equal to 40° C., for example a Tg ranging from 40 to 150° C., preferably greater than or equal to 50° C., ranging for example from 50° C. to 120° C. and better still greater than or equal to 60° C., ranging for example from 60° C. to 120° C. and/or monomers with a Tg of between 20 and 40° C., as described above.
- the block with a Tg of less than or equal to 20° C. is a homopolymer.
- the monomers whose homopolymer has a Tg of less than or equal to 20° C. are selected, preferably, from the following monomers, or principal monomer:
- R 3 representing a linear or branched C 1 to C 12 unsubstituted alkyl group, with the exception of the tert-butyl group, in which one or more heteroatoms selected from O, N and S is (are) optionally intercalated;
- R 4 representing a linear or branched C 6 to C 12 unsubstituted alkyl group, in which one or more hetero-atoms selected from O, N and S is (are) optionally intercalated;
- N—(C 4 to C 12 alkyl)acrylamides such as N-octylacrylamide
- the principal monomers that are particularly preferred for the block with a Tg of less than or equal to 20° C. are alkyl acrylates in which the alkyl chain contains from 1 to 10 carbon atoms, with the exception of the tert-butyl group, such as methyl acrylate, isobutyl acrylate and 2-ethylhexyl acrylate, and mixtures thereof.
- the block which has a Tg of between 20 and 40° C. may be a homopolymer or a copolymer.
- the block with a Tg of between 20 and 40° C. may be obtained totally or partly from one or more monomers which are such that the homopolymer prepared from these monomers has a glass transition temperature of between 20 and 40° C.
- the block with a Tg of between 20 and 40° C. may be obtained totally or partly from monomers which are such that the corresponding homopolymer has a Tg of greater than or equal to 40° C. and from monomers which are such that the corresponding homopolymer has a Tg of less than or equal to 20° C.
- this block is a homopolymer, it is obtained from monomers (or principal monomers) which are such that the homopolymers prepared from these monomers have glass transition temperatures of between 20 and 40° C.
- This first block may be a homopolymer composed of a single type of monomer (for which the Tg of the corresponding homopolymer ranges from 20° C. to 40° C.).
- the monomers whose homopolymer has a glass transition temperature of between 20 and 40° C. are selected, preferably, from n-butyl methacrylate, cyclodecyl acrylate, neopentyl acrylate and isodecylacrylamide, and mixtures thereof.
- the block with a Tg of between 20 and 40° C. is a copolymer, it is obtained totally or partly from one or more monomers (or principal monomers) the nature and concentration of which are selected such that the Tg of the resulting copolymer is between 20 and 40° C.
- the block with a Tg of between 20 and 40° C. is a copolymer obtained totally or partly from:
- Tg of greater than or equal to 40° C.
- a Tg ranging from 40° C. to 150° C., preferably greater than or equal to 50° C., ranging for example from 50 to 120° C. and better still greater than or equal to 60° C., ranging for example from 60° C. to 120° C., as described above;
- Such principal monomers are selected, for example, from methyl methacrylate, isobornyl acrylate and methacrylate, butyl acrylate and 2-ethylhexyl acrylate, and mixtures thereof.
- the proportion of the second block with a Tg of less than or equal to 20° C. ranges from 10% to 85%, better still from 20% to 70% and even better still from 20% to 50% by weight of the polymer.
- each of the first and second blocks comprises at least one monomer selected from acrylic acid, the esters of acrylic acid, (meth)acrylic acid, the esters of (meth)acrylic acid, and mixtures thereof.
- each of the first and second blocks is obtained totally from at least one monomer selected from acrylic acid, the esters of acrylic acid, (meth)acrylic acid, the esters of (meth)acrylic acid, and mixtures thereof.
- each of the blocks may contain in minority proportion at least one constituent monomer of the other block.
- first block may contain at least one constituent monomer of the second block, and vice versa.
- Each of the first and/or second blocks may comprise, in addition to the monomers indicated above, one or more other monomers known as additional monomers, which are different from the principal monomers mentioned above.
- This additional monomer is selected, for example, from:
- hydrophilic monomers such as:
- ethylenically unsaturated monomers comprising at least one carboxylic or sulphonic acid function, for instance: acrylic acid, methacrylic acid, crotonic acid, maleic anhydride, itaconic acid, fumaric acid, maleic acid, acrylamidopropanesulphonic acid, vinylbenzoic acid, vinylphosphoric acid, and salts thereof;
- ethylenically unsaturated monomers comprising at least one tertiary amine function, for instance 2-vinylpyridine, 4-vinylpyridine, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate and dimethylaminopropylmethacrylamide, and salts thereof;
- R 6 represents a linear or branched alkyl group containing from 1 to 4 carbon atoms, such as a methyl, ethyl, propyl or isobutyl group, the said alkyl group being substituted by one or more substituents selected from hydroxyl groups (for instance 2-hydroxypropyl methacrylate and 2-hydroxyethyl methacrylate) and halogen atoms (Cl, Br, I or F), such as trifluoroethyl methacrylate;
- R 9 representing a linear or branched C 6 to C 12 alkyl group in which one or more heteroatoms selected from O, N and S is (are) optionally intercalated, the said alkyl group being substituted by one or more substituents selected from hydroxyl groups and halogen atoms (Cl, Br, I or F);
- R 10 representing a linear or branched C 1 to C 12 alkyl group substituted by one or more substituents selected from hydroxyl groups and halogen atoms (Cl, Br, I or F), such as 2-hydroxypropyl acrylate and 2-hydroxyethyl acrylate, or R 10 represents a C 1 to C 12 alkyl-O-POE (polyoxyethylene) with repetition of the oxyethylene unit from 5 to 30 times, for example methoxy-POE, or R 10 represents a polyoxyethylenated group comprising from 5 to 30 ethylene oxide units;
- ethylenically unsaturated monomers comprising one or more silicon atoms, such as methacryloxypropyltrimethoxysilane and methacryloxypropyltris(trimethylsiloxy)silane;
- Additional monomers that are particularly preferred are acrylic acid, methacrylic acid and trifluoroethyl methacrylate, and mixtures thereof.
- each of the first and second blocks of the block polymer comprises at least one monomer selected from esters of (meth)acrylic acid and optionally at least one additional monomer such as (meth)acrylic acid, and mixtures thereof.
- each of the first and second blocks of the block polymer is obtained totally from at least one monomer selected from esters of (meth)acrylic acid and optionally at least one additional monomer such as (meth)acrylic acid, and mixtures thereof.
- the block polymer is a non-silicone polymer, i.e. a polymer free of silicon atoms.
- This or these additional monomer(s) generally represent(s) an amount of less than or equal to 30% by weight, for example from 1% to 30% by weight, preferably from 5% to 20% by weight and more preferably from 7% to 15% by weight, relative to the total weight of the first and/or second blocks.
- the block polymer may be obtained by free-radical solution polymerization according to the following preparation process:
- a portion of the polymerization solvent is introduced into a suitable reactor and heated until the adequate temperature for the polymerization is reached (typically between 60 and 120° C.),
- the constituent monomers of the first block are introduced in the presence of a portion of the polymerization initiator,
- the mixture is left to react for a time T′ (ranging from 3 to 6 hours), after which the mixture is cooled to ambient temperature,
- the block polymer comprises a first block with a Tg of greater than or equal to 40° C., as described above in a), and a second block with a Tg of less than or equal to 20° C., as described above in b).
- the first block with a Tg of greater than or equal to 40° C. is a copolymer obtained from monomers which are such that the homopolymer prepared from these monomers has a glass transition temperature of greater than or equal to 40° C., such as the monomers described above.
- the second block with a Tg of less than or equal to 20° C. is a homopolymer obtained from monomers which are such that the homopolymer prepared from these monomers has a glass transition temperature of less than or equal to 20° C., such as the monomers described above.
- the proportion of the block with a Tg of greater than or equal to 40° C. ranges from 20% to 90%, better still from 30% to 80% and even better still from 50% to 70% by weight of the polymer.
- the proportion of the block with a Tg of less than or equal to 20° C. ranges from 5% to 75%, preferably from 15% to 50% and better still from 25% to 45% by weight of the polymer.
- the polymer according to the invention may comprise:
- a first block with a Tg of greater than or equal to 40° C. for example having a Tg ranging from 70 to 110° C., which is a methyl methacrylate/acrylic acid copolymer,
- an intermediate block which is a methyl methacrylate/acrylic acid/methyl acrylate copolymer.
- the polymer according to the invention may comprise:
- an intermediate block which is a methyl methacrylate/acrylic acid/methyl acrylate/trifluoro-ethyl methacrylate random copolymer.
- the polymer according to the invention may comprise:
- an intermediate block which is an isobornyl acrylate/isobutyl methacrylate/2-ethylhexyl acrylate random copolymer.
- the polymer according to the invention may comprise:
- an intermediate block which is an isobornyl acrylate/methyl methacrylate/2-ethylhexyl acrylate random copolymer.
- the polymer according to the invention may comprise:
- an intermediate block which is an isobornyl acrylate/isobornyl methacrylate/2-ethylhexyl acrylate random copolymer.
- the polymer according to the invention may comprise:
- an intermediate block which is an isobornyl methacrylate/isobutyl methacrylate/isobutyl acrylate random copolymer.
- the polymer according to the invention may comprise:
- an intermediate block which is an isobornyl acrylate/isobornyl methacrylate/isobutyl acrylate random copolymer.
- the polymer according to the invention may comprise:
- an intermediate block which is an isobornyl acrylate/isobutyl methacrylate/isobutyl acrylate random copolymer.
- the amounts are expressed in grams.
- the mixture is held at 90° C. for 1 hour.
- the mixture is held at 90° C. for 3 hours, then diluted in 105 g of butyl acetate and 45 g of isopropanol, and then the whole is cooled.
- a polymer which comprises a first, poly(methyl methacrylate/acrylic acid) block with a Tg of 100° C., a second, polymethyl acrylate block with a Tg of 10° C., and an intermediate block which is a methyl methacrylate/acrylic acid/polymethyl acrylate random polymer.
- This polymer has a weight-average mass of 52 000 and a number-average mass of 18 000, giving a polydispersity index I of 2.89.
- the mixture is held at 90° C. for 1.5 h.
- the mixture is held at 90° C. for 3 hours and then the whole is cooled.
- a polymer which comprises a first, poly(isobornyl acrylate/isobutyl methacrylate) block with a Tg of 80° C., a second, poly-2-ethylhexyl acrylate block with a Tg of ⁇ 70° C., and an intermediate block which is an isobornyl acrylate/isobutyl methacrylate/2-ethylhexyl acrylate random polymer.
- This polymer has a weight-average mass of 77 000 and a number-average mass of 19 000, giving a polydispersity index I of 4.05.
- the mixture is held at 90° C. for 1.5 h.
- the mixture is held at 90° C. for 3 hours and then the whole is cooled.
- a polymer which comprises a first, poly(isobornyl acrylate/methyl methacrylate) block with a Tg of 100° C., a second, poly-2-ethylhexyl acrylate block with a Tg of ⁇ 70° C., and an intermediate block which is an isobornyl acrylate/methyl methacrylate/2-ethylhexyl acrylate random polymer.
- This polymer has a weight-average mass of 76 500 and a number-average mass of 22 000, giving a polydispersity index I of 3.48.
- the mixture is held at 90° C. for 1.5 h.
- the mixture is held at 90° C. for 3 hours and then the whole is cooled.
- a polymer which comprises a first, poly(isobornyl acrylate/isobornyl methacrylate) block or sequence with a Tg of 110° C., a second, poly-2-ethylhexyl acrylate block with a Tg of ⁇ 70° C., and an intermediate block which is an isobornyl acrylate/isobornyl methacrylate/2-ethylhexyl acrylate random polymer.
- This polymer has a weight-average mass of 103 900 and a number-average mass of 21 300, giving a polydispersity index I of 4.89.
- the block polymer comprises a first block with a glass transition temperature (Tg) of between 20 and 40° C., in accordance with the blocks described in c), and a second block with a glass transition temperature of less than or equal to 20° C., as described above in b), or a glass transition temperature of greater than or equal to 40° C., as described in a) above.
- Tg glass transition temperature
- the proportion of the first block with a Tg of between 20 and 40° C. ranges from 10% to 85%, better still from 30% to 80% and even better still from 50% to 70% by weight of the polymer.
- the second block is a block with a Tg of greater than or equal to 40° C., it is preferably present in a proportion ranging from 10% to 85% by weight, better still from 20% to 70% and even better still from 30% to 70% by weight of the polymer.
- the second block is a block with a Tg of less than or equal to 20° C., it is preferably present in a proportion ranging from 10% to 85% by weight, better still from 20% to 70% and even better still from 20% to 50% by weight of the polymer.
- the first block with a Tg of between 20 and 40° C. is a copolymer obtained from monomers which are such that the corresponding homopolymer has a Tg of greater than or equal to 40° C., and from monomers which are such that the corresponding homopolymer has a Tg of less than or equal to 20° C.
- the second block with a Tg of less than or equal to 20° C. or with a Tg of greater than or equal to 40° C. is a homopolymer.
- the block polymer may comprise:
- an intermediate block comprising at least one methyl acrylate or methyl methacrylate monomer
- an intermediate block comprising methyl methacrylate, at least one acrylic acid monomer and at least one methyl acrylate monomer.
- the block polymer may comprise:
- an intermediate block which is an isobornyl acrylate/isobutyl methacrylate/2-ethylhexyl acrylate random copolymer.
- the block polymer may comprise:
- an intermediate block which is an isobornyl acrylate/methyl acrylate/acrylic acid random copolymer.
- the polymers corresponding to this second embodiment may be realised as follows.
- the mixture is held at 90° C. for 1 hour.
- the mixture is held at 90° C. for 3 hours and then diluted with 105 g of butyl acetate and 45 g of isopropanol, and the whole is then cooled.
- the polymer obtained comprises a first poly(methyl acrylate/methyl methacrylate/acrylic acid) block having a Tg of 35° C., a second poly(methyl methacrylate) block having a Tg of 100° C. and an intermediate block which is a methyl methacrylate/acrylic acid/polymethyl acrylate random polymer.
- the mixture is held at 90° C. for 1.5 h.
- the mixture is held at 90° C. for 3 hours and then diluted and the whole is then cooled.
- a polymer which comprises a first poly(isobornyl acrylate/isobutyl methacrylate/2-ethyl-hexyl acrylate) block having a Tg of 25° C., a second poly-2-ethylhexyl acrylate block having a Tg of ⁇ 50° C. and an intermediate block which is an isobornyl acrylate/isobutyl methacrylate/2-ethylhexyl acrylate random polymer.
- composition according to the invention contains preferably from 0.1% to 60% by weight of active substance (or solids) of the polymer, preferably from 0.5% to 50% by weight and more preferably from 1% to 40% by weight.
- the composition of the invention also comprises at least one agent for gelling the organic liquid medium of the composition.
- the gelling agent may increase the viscosity of the organic liquid medium and may lead to a solid or flowable composition when introduced into the said organic liquid medium.
- the gelling agent may be selected from gelling agents in polymeric form and gelling agents in mineral form.
- the gelling agent is not soluble in an aqueous phase or in water.
- the gelling agent according to the present invention is selected preferably from the group consisting of agents which gel via chemical crosslinking and agents which gel via physical crosslinking.
- crosslinked elastomeric polyorganosiloxanes of three-dimensional structure such as MQ silicone resins, polyalkylsesquioxanes, especially polymethyl-sesquioxanes, and resins crosslinked via hydro-silylation.
- silicone resins may carry hydrophilic groups, such as polyoxyethylene or copoly(oxyethylene/oxypropylene).
- polyorganosiloxanes comprising R 2 SiO and RSiO 1.5 units and optionally R 3 SiO 0.5 and/or SiO 2 units, in which the radicals R 1 , independently of one another, are selected from a hydrogen, an alkyl such as methyl, ethyl or propyl, an aryl such as phenyl or tolyl, an unsaturated aliphatic group such as vinyl, the weight ratio of the units R 2 SiO to the units RSiO 1.5 ranging from 1/1 to 30/1;
- polyorganosiloxanes which are insoluble and swellable in silicone oil, obtained by addition of a polyorganohydrosiloxane (1) and a polyorganosiloxane (2) having unsaturated aliphatic groups such that the amount of hydrogen or of unsaturated aliphatic groups in (1) and (2) respectively ranges from 1 to 20 mol % when the polyorganosiloxane is non-cyclic and from 1 to 50 mol % when the polyorganosiloxane is cyclic.
- these polyorganosiloxanes can comprise from 1 to 40 oxyalkylene groups, such as oxypropylene and/or oxyethylene groups.
- Gelling agents which gel via physical crosslinking, particularly by molecular agitation, hydrogen interactions or dipolar interactions, and also fat-soluble polymers having liquid crystal groups, are preferred.
- Gelling agents which gel via molecular agitation are polymers having high molecular weights, preferably greater than 500 000, such as silicone gums.
- the silicone gum may correspond to the formula: in which:
- silicone gums which can be used as a gelling agent according to the invention, mention may be made of those for which:
- the substituents R 7 to R 12 represent a methyl group
- the substituent X represents a hydroxyl group
- the substituents R 7 to R 12 represent a methyl group
- the substituent X represents a hydroxyl group
- the substituents R 7 , R 8 , R 11 , R 12 and X represent a methyl group and the substituents R 9 and R 10 represent an aryl group, such that the molecular weight of the gum is approximately 600 000, for example the product sold or made under the name 761 by the company Rhöne-Poulenc (Rhodia Chimie).
- Gelling agents which gel the organic liquid medium via hydrogen interactions are selected preferably from the group consisting of:
- aminosilicone polymers having triazinyl groups or pyrimidinyl groups bonded to amino groups of aminosilicones, as described in patent application EP 0 751 170, the disclosure of which is incorporated in this text by reference,
- non-silicone polyamides whose ends carry ester or triamide functions, such as the compounds described in patents and patent applications U.S. Pat. No. 5,783,657, U.S. Pat. No. 6,268,466, WO 01/95871, WO 00/40216, U.S. Pat. No. 2002/0035237 and EP 1 068 856, the disclosure of which is incorporated in this text by reference,
- polyurethanes such as the compounds described in patent applications DE 100 22 247 and FR 2 814 365, the disclosure of which is incorporated in this text by reference, and
- vinyl and/or (meth)acrylic polymers carrying side groups which are able to give rise to mutual hydrogen interactions such as the compounds described in patent application WO 93/01797, the disclosure of which is incorporated in this text by reference.
- Gelling agents may also be selected from the group consisting of:
- copolymers such as polystyrene-silicone or polyethylene-silicone, described in patents U.S. Pat. No. 6,225,390, U.S. Pat. No. 6,160,054, U.S. Pat. No. 6,174,968 and U.S. Pat. No. 6,225,390, the disclosures of which are incorporated in this text by reference,
- copolymers comprising a silicone block and another block or graft which is polyvinylic or poly(meth)acrylic, such as those described in patents U.S. Pat. No. 5,468,477 and U.S. Pat. No. 5,725,882, the disclosures of which are incorporated in this text by reference,
- the ethylenic gelling agent may comprise, for example, a styrene (S) block and an alkylstyrene (AS) block, and a block selected from ethylene/butylene (EB), ethylene/propylene (EP), butadiene (B), isoprene (I), acrylate (A) and methacrylate (MA) blocks or a combination of these blocks.
- S styrene
- AS alkylstyrene
- EB ethylene/butylene
- EP ethylene/propylene
- B butadiene
- I isoprene
- A acrylate
- MA methacrylate
- a copolymer comprising at least one styrene block is used as gelling agent.
- a triblock copolymer and in particular those of the polystyrene/polyisoprene or polystyrene/polybutadiene type, such as those sold or made under the name “Luvitol HSB” by BASF and those of the polystyrene/copoly(ethylene-propylene) type or, alternatively, those of the polystyrene/copoly(ethylene/butylene) type, such as those sold or made under the brand name “Kraton” by Shell Chemical Co. or Gelled Permethyl 99A by Penreco, may be used. Styrene-methacrylate copolymers may also be used.
- SEBS Kraton G1650
- SEBS Kraton G1651
- SEBS Kraton G1652
- SEBS Kraton G1657
- Diblocks or triblocks such as polystyrene-copoly(ethylene/propylene) or polystyrene-copoly(ethylene/butylene), such as those described in patent applications WO 98/38981 and US 2002/0055562 are also included in the present invention.
- Gelling agents which gel via dipolar interactions are selected preferably from the compounds described in documents WO 01/30886 and U.S. Pat. No. 6,228,967, the disclosures of which are incorporated in this text by reference.
- the ionized groups in the said compounds for example the zwitterionic groups, create the said dipolar interactions.
- Gelling agents such as the fat-soluble polymers having liquid crystal groups are also preferred according to the present invention, particularly fat-soluble polymers whose skeleton is of silicone, vinyl and/or (meth)acrylic type, and which possess liquid crystal side groups, especially the compounds described in patent application FR 2 816 503, the disclosure of which is incorporated in this text by reference.
- the gelling agent may be in mineral form.
- the gelling agent may be a modified clay.
- modified clays which can be used, mention may be made of hectorites modified with an ammonium chloride of a C 10 to C 22 fatty acid, such as a hectorite modified with distearyldimethylammonium chloride, also known as bentonite of quaternium-18, such as the products sold or made under the names Bentone 34 by the company Rheox, Claytone XL, Claytone 34 and Claytone 40 sold or made by the company Southern Clay, modified clays known under the name quaternium-18 bentonites and benzalkonium bentonites and sold or made under the names Claytone HT, Claytone GR and Claytone PS by the company Southern Clay, clays modified with stearyldimethylbenzoylammonium chloride, known as stearalkonium bentonites, such as the products sold or made under the names Claytone APA and Claytone AF by the company Southern Clay, and Baragel 24, sold or made by the company Rheox
- silica such as fumed silica.
- the fumed silica may have a particle size which may be nanometric or micrometric, for example ranging from approximately 5 nm to 200 nm.
- Fumed silicas may be obtained by high-temperature hydrolysis of a volatile silicon compound in an oxyhydrogen flame, producing a finely divided silica. This process allows hydrophilic silicas to be obtained which possess a large number of silanol groups on their surface.
- the silanol groups may be replaced, for example, by hydrophobic groups: this then gives a hydrophobic silica.
- the hydrophobic groups may be:
- silica silylate according to the CTFA (6th edition, 1995). They are sold or made, for example, under the references “Aerosil R812®” by the company Degussa, and “CAB-O-SIL TS-530® by the company Cabot;
- dimethylsilyloxyl or polydimethylsiloxane groups which are obtained in particular by treating fumed silica in the presence of polydimethyldisiloxane or dimethyldichlorosilane.
- the silicas thus treated are known as “silica dimethylsilylate” according to the CTFA (6th edition, 1995). They are sold or made, for example, under the references “Aerosil R972®” and “Aerosil R974®” by the company Degussa, and “CAB-O-SIL TS-610®” and “CAB-O-SIL TS-720®” by the company Cabot;
- hydrophobic silica such as a fumed silica, may be used as gelling agent.
- the gelling agent may be used, for example, in concentrations ranging from 0.05% to 35% of the total weight of the composition, for example from 0.5% to 20% or from 1% to 10%.
- composition according to the invention may comprise a hydrophilic medium comprising water or a mixture of water and hydrophilic organic solvent(s) such as alcohols and especially linear or branched lower monoalcohols having from 2 to 5 carbon atoms such as ethanol, isopropanol or n-propanol, and polyols such as glycerol, diglycerol, propylene glycol, sorbitol, pentylene glycol, and polyethylene glycols, or else C 2 ethers and C 2 -C 4 aldehydes which are hydrophilic.
- hydrophilic medium comprising water or a mixture of water and hydrophilic organic solvent(s) such as alcohols and especially linear or branched lower monoalcohols having from 2 to 5 carbon atoms such as ethanol, isopropanol or n-propanol, and polyols such as glycerol, diglycerol, propylene glycol, sorbitol, pentylene glycol, and
- the water or the mixture of water and hydrophilic organic solvents may be present in the composition according to the invention in an amount ranging from 0.1% to 99% by weight, relative to the total weight of the composition, and preferably from 10% to 80% by weight.
- composition according to the invention comprises an organic liquid medium which is cosmetically acceptable (acceptable tolerance, toxicology and feel).
- the organic liquid medium of the composition comprises at least one organic solvent, which is the, or one of the, polymerization solvent(s) of the block polymer as described above.
- the said organic solvent is the majority liquid by weight in the organic liquid medium of the cosmetic composition.
- the organic liquid medium comprises fatty substances which are liquid at ambient temperature (25° C. in general). These liquid fatty substances may be animal, vegetable, mineral or synthetic in origin.
- oils which can be used in the invention mention may be made of: hydrocarbon oils of animal origin, such as perhydrosqualene; vegetable hydrocarbon oils, such as liquid triglycerides of fatty acids of 4 to 10 carbon atoms, such as heptanoic or octanoic acid triglycerides, or else sunflower oil, corn oil, soya oil, grape seed oil, sesame oil, apricot oil, macadamia oil, castor oil, avocado oil, caprylic/capric acid triglycerides, jojoba oil, karite butter; linear or branched hydrocarbons, of mineral or synthetic origin, such as liquid paraffins and derivatives thereof, Vaseline, polydecenes, hydrogenated polyisobutene such as butter; the synthetic esters and ethers particularly of fatty acids, such as, for example, purcellin oil, isopropyl myristate, 2-ethylhexyl
- oils may be present in an amount ranging from 0.01% to 90%, and better still from 0.1% to 85% by weight, relative to the total weight of the composition.
- the organic liquid medium of the composition according to the invention may also comprise one or more organic solvents which are cosmetically acceptable (acceptable tolerance, toxicology and feel).
- solvents may be generally present in an amount ranging from 0.1% to 90%, more preferably from 10% to 90% by weight, relative to the total weight of the composition, and better still from 30% to 90%.
- solvents which can be used in the composition of the invention mention may be made, besides the aforementioned hydrophilic organic solvents, of ketones which are liquid at ambient temperature, such as methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, isophorone, cyclohexanone and acetone; propylene glycol ethers which are liquid at ambient temperature, such as propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and dipropylene glycol mono-n-butyl ether; short-chain esters (having 3 to 8 carbon atoms in total), such as ethyl acetate, methyl acetate, propyl acetate, n-butyl acetate and isopentyl acetate; ethers which are liquid at ambient temperature, such as diethyl ether, dimethyl ether or dichlorodiethyl ether; alkanes which are liquid at ambient temperature,
- the composition may comprise an additional polymer such as a film-forming polymer.
- a “film-forming polymer” is a polymer capable of forming, by itself or in the presence of an auxiliary film-forming agent, a continuous and adherent film on a support, particularly on keratin materials.
- film-forming polymer mention may be made in particular of acrylic polymers, polyurethanes, polyesters, polyamides, polyureas and cellulosic polymers such as nitro-cellulose.
- the polymer may be combined with one or more auxiliary film-forming agents.
- a film-forming agent of this kind may be selected from all of the compounds known to the person skilled in the art as being capable of fulfilling the desired function, and in particular may be selected from plasticizers and coalescers.
- composition according to the invention may include at least one wax.
- wax in the sense of the present invention is meant a lipophilic compound which is solid at ambient temperature (25° C.), exhibits a reversible solid/liquid state change and has a melting point greater than or equal to 30° C. and possibly up to 120° C.
- the melting point of the wax can be measured by means of a differential scanning calorimeter (DSC), an example being the calorimeter sold under the name DSC 30 by the company Mettler.
- DSC differential scanning calorimeter
- the waxes may be hydrocarbon waxes, fluoro waxes and/or silicone waxes and may be vegetable, mineral, animal and/or synthetic in origin.
- the waxes have a melting point of more than 25° C. and better still more than 45° C.
- wax which can be used in the composition of the invention mention may be made of beeswax, carnauba wax or candelilla wax, paraffin, microcrystalline waxes, ceresin or ozokerite; synthetic waxes such as polyethylene waxes or Fischer-Tropsch waxes, and silicone waxes such as the alkyl- or alkoxydimethicones having 16 to 45 carbon atoms.
- the nature and amount of the solid fatty substances are a function of the desired mechanical properties and textures.
- the composition may contain from 0% to 50% by weight of waxes, relative to the total weight of the composition, and better still from 1% to 30% by weight.
- composition according to the invention may further comprise one or more colorants selected from water-soluble dyes and pulverulent colorants such as pigments, nacres and flakes, which are well known to the person skilled in the art.
- the colorants may be present in the composition in an amount ranging from 0.01% to 50% by weight, relative to the weight of the composition, preferably from 0.01% to 30% by weight.
- pigments are meant particles of any form, white or coloured, organic or inorganic, which are insoluble in the physiological medium and are intended for colouring the composition.
- nacres are meant iridescent particles of any form that are produced in particular by certain molluscs in their shell, or else are synthesized.
- the pigments may be white or coloured, organic and/or inorganic.
- inorganic pigments mention may be made of titanium dioxide, optionally in surface-treated form, zirconium oxide or cerium oxide, and also zinc oxide, iron oxides (black, yellow or red) or chromium oxide, manganese violet, ultramarine blue, chromium hydrate and ferric blue, and metal powders such as aluminium powder and copper powder.
- organic pigments mention may be made of carbon black, D & C pigments, and the cochineal carmine-based lakes of barium, strontium, calcium and aluminium.
- effect pigments such as particles comprising an organic or inorganic, natural or synthetic substrate, for example glass, acrylic resins, polyester, polyurethane, polyethylene terephthalate, ceramics or aluminas, the said substrate being uncovered or covered with metallic substances such as aluminium, gold, silver, platinum, copper or bronze, or with metal oxides such as titanium dioxide, iron oxide or chromium oxide, and mixtures thereof.
- the nacreous pigments may be selected from white nacreous pigments such as titanium-covered mica, or bismuth oxychloride, coloured nacreous pigments such as titanium mica covered with iron oxides, titanium mica covered with, in particular, ferric blue or chromium oxide, titanium mica covered with an organic pigment of the aforementioned type, and also nacreous pigments based on bismuth oxychloride. It is also possible to use interference pigments, especially those which are liquid-crystal pigments or multi-layer pigments.
- the water-soluble dyes are, for example, beetroot juice and methylene blue.
- composition according to the invention may further comprise one or more fillers, particularly in an amount ranging from 0.01% to 50% by weight, relative to the total weight of the composition, preferably ranging from 0.01% to 30% by weight.
- fillers are meant particles of any form, colourless or white, mineral or synthetic, which are insoluble in the medium of the composition irrespective of the temperature at which the composition is manufactured. These fillers serve in particular to modify the rheology or texture of the composition.
- the fillers may be organic or inorganic and may be in any form, platelet-shaped, spherical or oblong, irrespective of the crystallographic form (for example leaf, cubic, hexagonal, orthorhombic, etc.). Mention may be made of talc, mica, silica, kaolin, polyamide (Nylon®) powders (Orgasol® from Atochem), poly- ⁇ -alanine and polyethylene, the powders of polymers of tetrafluoroethylene (Teflon®), lauroyl-lysine, starch, boron nitride, hollow polymeric microspheres such as those of polyvinylidene chloride/acrylonitrile, for instance Expancel® (Nobel Industrie), acrylic acid copolymers (Polytrap® from the company Dow Corning) and silicone resin microbeads (Tospearls® from Toshiba, for example), elastomeric polyorganosiloxane particles, precipitated calcium carbonate, magnesium carbon
- the composition according to the invention may be in the form in particular of a stick, suspension, dispersion, solution, gel, emulsion, especially oil-in-water (O/W) or water-in-oil (W/O), or multiple (O/W/O or polyol/O/W or W/O/W), emulsion, or in the form of a cream, paste or mousse, or a vesicle dispersion, particularly of ionic or nonionic lipids, or a two-phase or multi-phase lotion, a spray, powder or paste, especially a flexible paste (in particular a paste having a dynamic viscosity at 25° C. of the order of 0.1 to 40 Pa ⁇ s at a shear rate of 200 s ⁇ 1 , after 10 minutes of measurement in cone/plate geometry).
- the composition may be anhydrous: for example, it may be an anhydrous paste.
- composition according to the invention may be a makeup composition such as products for the complexion (foundations), rouges, eyeshadows, lipsticks, concealers, blushers, mascaras, eyeliners, eyebrow makeup products, lip pencils, eye pencils, nail products, such as nail varnishes, body makeup products or hair makeup products (hair lacquer or mascara).
- a makeup composition such as products for the complexion (foundations), rouges, eyeshadows, lipsticks, concealers, blushers, mascaras, eyeliners, eyebrow makeup products, lip pencils, eye pencils, nail products, such as nail varnishes, body makeup products or hair makeup products (hair lacquer or mascara).
- composition according to the invention may also be a facial or bodily skincare product, in particular a sun product or skin colouring product (such as a self-tanning product).
- the present invention likewise provides a cosmetic kit comprising:
- composition as described above disposed inside the said compartment.
- the container may be in any appropriate form. It may in particular be in the form of a bottle, tube, jar, case, box, sachet or carton.
- the closing element may be in the form of a removable stopper, a lid, a cap, a tear-off strip or a capsule, particularly of the type comprising a body attached to the container and a cover cap articulated on the body. It may also be in the form of an element for selectively closing the container, particularly a pump, valve or valve flap.
- the container may be combined with an applicator, particularly in the form of a brush comprising an arrangement of bristles held by a twisted wire.
- a twisted brush of this kind is described in particular in patent U.S. Pat. No. 4,887,622. It may also be in the form of a comb comprising a plurality of application elements, obtained in particular from moulding. Combs of this kind are described, for example, in patent FR 2 796 529.
- the applicator may be in the form of a fine brush, as described, for example, in patent FR 2 722 380.
- the applicator may be in the form of a block of foam or elastomer, a felt or a spatula.
- the applicator may be free (tuft or sponge) or of one piece with a rod carried by the closing element, as described, for example, in patent U.S. Pat. No. 5,492,426.
- the applicator may be of one piece with the container, as described, for example, by patent FR 2 761 959.
- the product may be accommodated directly in the container, or indirectly.
- the product may be arranged on an impregnated support, particularly in the form of a wipe or pad, and arranged (in unitary or plural form) in a box or in a sachet.
- a support of this kind, incorporating the product, is described for example in patent application WO 01/03538.
- the closing element may be coupled to the container by screwing.
- the coupling between the closing element and the container is performed other than by screwing, in particular via a bayonet mechanism, by snap-fastening, gripping, welding, adhesive bonding, or by magnetic attraction.
- snap-fastening is meant, in particular, any system involving the traversal of a bead or cord of material by elastic deformation of a portion, particularly of the closing element, followed by return to the elastically unstressed position of the said portion after the traversal of the bead or cord.
- the container may be at least partly made of thermoplastic material.
- thermoplastic materials include polypropylene and polyethylene.
- the container is made of a non-thermoplastic material, particularly of glass or of metal (or alloy).
- the container may be one with rigid walls or may have deformable walls, particularly in the form of a tube or tubular bottle.
- the container may include means intended for distributing, or facilitating the distribution of, the composition.
- the container may have walls which are deformable so as to allow the composition to exit in response to a positive pressure inside the container, this positive pressure being brought about by elastic (or non-elastic) squeezing of the container's walls.
- the product may be driven by a piston mechanism.
- the container may include a mechanism, especially a rack mechanism, or one with a threaded rod, or with a helical groove, which is capable of displacing a stick in the direction of the said opening.
- a mechanism of this kind is described for example in patent FR 2 806 273 or in patent FR 2 775 566.
- a mechanism of this kind for a liquid product is described in patent FR 2 727 609.
- the container may be composed of a carton with a base delimiting at least one housing accommodating the composition, and a lid, particularly a lid articulated on the base, which is capable of covering the said base, at least in part.
- a carton of this kind is described for example in patent application WO 03/018423 or in patent FR 2 791 042.
- the container may be equipped with a drainer arranged in the region of the opening of the container.
- a drainer of this kind allows the applicator to be wiped and optionally allows the rod, which may be of one piece with it, to be wiped.
- a drainer of this kind is described for example in patent FR 2 792 618.
- the composition may be at the atmospheric pressure inside the container (at ambient temperature) or may be in pressurized form, particularly by means of a propellent gas (aerosol). In the latter case the container is equipped with a valve (of the type used for aerosols).
- the formula exhibits a much greater viscosity than the reference without gelling agent. It can also be applied without difficulty using a foam applicator, and leads to a homogeneous deposit.
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Abstract
Description
- The present invention relates to a cosmetic composition for making up or caring for human bodily and facial skin, the scalp included, the lips or epidermal derivatives of human beings, such as the hair, eyebrows, eyelashes or nails, which comprises a particular block polymer.
- The composition may be a loose or compact powder, a foundation, a rouge, an eyeshadow, a concealer, a blusher, a lipstick, a lip balm, a lipgloss, a lip pencil, an eye pencil, a mascara, an eyeliner, a nail varnish or even a body makeup product or a skin colouring product.
- Known compositions exhibit poor staying power over time, particularly as regards the colour. This poor staying power is characterized by an alteration in colour (colour change, fading), generally as a result of interaction with the sebum and/or perspiration secreted by the skin, in the case of foundation and of rouge or eyeshadow, or of interaction with the saliva, in the case of lipsticks. This alteration obliges the user to apply fresh makeup at frequent intervals, which may constitute a loss of time.
- So-called “non-transfer” makeup compositions for the lips and skin are compositions which have the advantage of forming a deposit which at least in part is not deposited on the supports with which they are brought into contact (glass, clothing, cigarette, fabrics).
- Known non-transfer compositions are generally based on silicone resins and volatile silicone oils and, although exhibiting improved staying properties, have the drawback of leaving on the skin and lips, following evaporation of the volatile silicone oils, a film which over time becomes uncomfortable (giving sensations of drying and tightening), thereby distancing a certain number of women from this type of lipstick.
- Known non-transfer compositions contain volatile oils in association with film-forming polymers, which may be soluble in the oils, so as to limit the transfer of colour. The introduction of these polymers in solution in volatile solvents, however, has the disadvantage of leading to formulas which are sometimes of low viscosity, owing in particular to the use of oil of very low viscosity and, in particular, of volatile oils. This low rheology goes hand in hand with awkward and unattractive application, with the added factor that the drying due to the presence of the volatiles may fix these inhomogeneities of deposition.
- There continues to be a need for a cosmetic product which should at one and the same time be a non-transfer product with good staying power and good texture which is easy to apply and leads to a homogeneous deposit.
- The composition of the invention may in particular constitute a product for making up the body, the lips or the epidermal derivatives of human beings which has, in particular, non-therapeutic treatment and/or care properties. It constitutes in particular a lipstick or a lipgloss, a rouge or eyeshadow, a tattooing product, a mascara, an eyeliner, a nail varnish, an artificial skin-tanning product or a hair colouring or haircare product.
- Surprisingly the inventors have found that a composition comprising a cosmetically acceptable organic liquid medium, at least one particular block polymer and a gelling agent for the said medium exhibits good spreading and lubricity properties and allows a homogeneous makeup result to be obtained. Moreover, the composition is glossy, does not transfer and has good staying power.
- More specifically the invention provides first a cosmetic composition comprising, in a cosmetically acceptable organic liquid medium, at least one non-elastomeric film-forming ethylenic linear block polymer and a gelling agent for the said organic liquid medium.
- The present invention likewise provides a cosmetic composition comprising, in a cosmetically acceptable organic liquid medium, at least one film-forming ethylenic linear block polymer free from styrene units, and a gelling agent for the said organic liquid medium.
- The invention also relates to a method of making up the skin and/or the lips and/or the epidermal derivatives which consists in applying to the skin and/or the lips and/or the epidermal derivatives the composition as defined above.
- The composition according to the invention may be applied to the skin of the face, the scalp and the body, the mucosae such as the lips, the inside of the lower eyelids, and the epidermal derivatives such as the nails, eyebrows, hair, eyelashes, and even body hair.
- Preferably the composition according to the invention is not a rinse-off composition.
- The invention likewise relates to the cosmetic use of the composition defined above for enhancing the homogeneity of makeup on the skin and/or the lips and/or the epidermal derivatives.
- The invention provides finally for the use of a gelling agent in a composition comprising a block polymer as described above for the purpose of obtaining a composition which has good texture, is easy to apply and leads to a deposit which is glossy, does not migrate and/or has good staying power and/or is homogeneous.
- Block Polymer:
- The composition according to the present invention comprises at least one block polymer. By “block” polymer is meant a polymer comprising at least 2 distinct blocks, preferably at least 3 distinct blocks.
- According to one embodiment the block polymer of the composition according to the invention is an ethylenic polymer. By “ethylenic” polymer is meant a polymer obtained by polymerizing monomers comprising an ethylenic unsaturation.
- According to one embodiment the block polymer of the composition according to the invention is a linear polymer. By opposition, a polymer having a non-linear structure is, for example, a polymer having a branched, starburst, graft or other structure.
- According to one embodiment the block polymer of the composition according to the invention is a film-forming polymer. By “film-forming” polymer is meant a polymer capable of forming, by itself or in the presence of an auxiliary film-forming agent, a continuous and adherent film on a support, particularly on keratin materials.
- According to one embodiment the block polymer of the composition according to the invention is a non-elastomeric polymer.
- By “non-elastomeric polymer” is meant a polymer which, when subjected to a stress intended to stretch it (for example by 30% relative to its initial length), does not return to a length substantially identical to its initial length when the stress ceases.
- More specifically the term “non-elastomeric polymer” denotes a polymer having an instantaneous recovery Ri<50% and a retarded recovery R2h<70% after having undergone 30% elongation. Preferably Ri is <30% and R2h is <50%.
- More specifically the non-elastomeric character of the polymer is determined in accordance with the following protocol:
- A polymer film is prepared by pouring a solution of the polymer into a Teflon-coated mould and then drying it for 7 days in an environment controlled at 23±5° C. and 50±10% relative humidity.
- This gives a film approximately 100 μm thick, from which rectangular specimens are cut (using a punch, for example) 15 mm wide and 80 mm long.
- This sample is subjected to a tensile stress by means of an apparatus sold under the reference Zwick, under the same temperature and humidity conditions as for drying.
- The specimens are stretched at a speed of 50 mm/min, and the distance between the jaws is 50 mm, corresponding to the initial length (l0) of the specimen.
- The instantaneous recovery Ri is determined as follows:
- the specimen is stretched by 30% (εmax), i.e. about 0.3 times its initial length (l0);
- the stress is released by applying a return speed equal to the tensile speed, i.e. 50 mm/min, and the residual elongation of the specimen is measured as a percentage, after return to zero stress (εi).
- The instantaneous recovery in % (Ri) is given by the formula below:
R i=(εmax−εi)/εmax)×100 - To determine the retarded recovery the residual elongation of the specimen is measured as a percentage (ε2h) 2 hours after return to zero stress.
- The retarded recovery in % (R2h) is given by the formula below:
R 2h=(εmax−ε2h)/εmax)×100 - Purely by way of indication, a polymer according to one embodiment of the invention possesses an instantaneous recovery Ri of 10% and a retarded recovery R2h of 30%.
- According to another embodiment the block polymer of the composition according to the invention does not include a styrene unit. By polymer free from styrene units is meant a polymer containing less than 10%, preferably less than 5%, preferably less than 2%, more preferably less than 1% by weight i) of styrene unit of formula —CH(C6H5)—CH2— or ii) of substituted styrene unit, for example methylstyrene, chlorostyrene or chloromethylstyrene.
- According to one embodiment the block polymer of the composition according to the invention is obtained from aliphatic ethylenic monomers. By aliphatic monomer is meant a monomer containing no aromatic group.
- According to one embodiment the block polymer is an ethylenic polymer obtained from aliphatic ethylenic monomers comprising a carbon-carbon double bond and at least one ester group —COO— or amide group —CON—. The ester group may be bonded to one of the two unsaturated carbons via the carbon atom or the oxygen atom. The amide group may be bonded to one of the two unsaturated carbons via the carbon atom or the nitrogen atom.
- According to one mode of implementation the block polymer comprises at least one first block and at least one second block.
- By “at least” one block is meant one or more blocks.
- It is specified that, in the text above and below, the terms “first” and “second” blocks in no way condition the order of the said blocks (or sequences) in the structure of the polymer.
- According to one mode of implementation the block polymer comprises at least one first block and at least one second block which have different glass transition temperatures (Tgs).
- In this mode of implementation the first and second blocks may be connected to one another by an intermediate segment having a glass transition temperature between the glass transition temperatures of the first and second blocks.
- According to one mode of implementation the block polymer comprises at least one first block and at least one second block connected to one another by an intermediate segment comprising at least one constituent monomer of the first block and at least one constituent monomer of the second block.
- Preferably the intermediate block is obtained essentially from constituent monomers of the first block and of the second block.
- By “essentially” is meant to an extent of at least 85%, preferably at least 90%, more preferably 95% and more preferably still 100%.
- Advantageously the intermediate segment comprising at least one constituent monomer of the first block and at least one constituent monomer of the second block of the polymer is a random polymer.
- According to one mode of implementation the block polymer comprises at least one first block and at least one second block which are incompatible in the organic liquid medium of the composition of the invention.
- By “blocks incompatible with one another” is meant that the mixture formed from the polymer corresponding to the first block and from the polymer corresponding to the second block is not miscible in the liquid that is in a majority by weight in the organic liquid medium of the composition, at ambient temperature (25° C.) and atmospheric pressure (105 Pa), for a polymers mixture content greater than or equal to 5% by weight, relative to the total weight of the mixture (polymers and majority organic liquid), with the provisos that
- i) the said polymers are present in the mixture in an amount such that the respective weight ratio ranges from 10/90 to 90/10, and that
- ii) each of the polymers corresponding to the first and second blocks has an average molecular mass (by weight or by number) equal to that of the block polymer±15%.
- In the case where the organic liquid medium comprises a mixture of organic liquids, should two or more liquids be present in identical mass proportions, the said polymers mixture is not miscible in at least one of them.
- In the case where the organic liquid medium comprises a single organic liquid, the said liquid, quite obviously, constitutes the liquid that is in a majority by weight.
- By “organic liquid medium” is meant a medium comprising at least one organic liquid, in other words at least one organic compound which is liquid at ambient temperature (25° C.) and atmospheric pressure (105 Pa). According to one mode of implementation the majority liquid of the organic liquid medium is a volatile or non-volatile oil (fat). Preferably the organic liquid is cosmetically acceptable (acceptable tolerance, toxicology and feel). The organic liquid medium is cosmetically acceptable in the sense that it is compatible with keratin materials, such as the oils or organic solvents commonly employed in cosmetic compositions.
- According to one mode of implementation the majority liquid of the organic liquid medium is the polymerization solvent or one of the polymerization solvents of the block polymer, as are described below.
- By polymerization solvent is meant a solvent or a mixture of solvents. The polymerization solvent may be selected in particular from ethyl acetate, butyl acetate, alcohols such as isopropanol and ethanol, aliphatic alkanes such as isododecane, and mixtures thereof. Preferably the polymerization solvent is a mixture of butyl acetate and isopropanol, or isododecane.
- Generally speaking, the block polymer may be incorporated into the composition at a high solids content, typically more than 10%, more than 20% and more preferably more than 30% and more preferably still more than 45% by weight relative to the total weight of the composition, while being easy to formulate.
- Preferentially the block polymer does not include silicon atoms in its skeleton. By “skeleton” is meant the main chain of the polymer, as opposed to the pendent side chains.
- Preferably the polymer according to the invention is not water-soluble, which is to say that the polymer is not soluble in water or in a mixture of water and linear or branched lower monoalcohols having 2 to 5 carbon atoms, such as ethanol, isopropanol or n-propanol, without a change in pH, at an active substance content of at least 1% by weight, at ambient temperature (25° C.).
- According to one mode of implementation the block polymer has a polydispersity index I of greater than 2.
- Advantageously the block polymer used in the compositions according to the invention has a polydispersity index I of greater than 2, ranging for example from 2 to 9, preferably greater than or equal to 2.5, ranging for example from 2.5 to 8, and better still greater than or equal to 2.8, and in particular ranging from 2.8 to 6.
- The polydispersity index I of the polymer is equal to the ratio of the weight-average mass Mw to the number-average mass Mn.
- The weight-average (Mw) and number-average (Mn) molar masses are determined by liquid chromatography by gel permeation (THF solvent, calibration curve established with standards of linear polystyrene, refractometric detector).
- The weight-average mass (Mw) of the block polymer is preferably less than or equal to 300 000, and ranges for example from 35 000 to 200 000, better still from 45 000 to 150 000.
- The number-average mass (Mn) of the block polymer is preferably less than or equal to 70 000, and ranges for example from 10 000 to 60 000, better still from 12 000 to 50 000.
- Each block or sequence of the block polymer is obtained from one type of monomer or from two or more different types of monomers.
- This signifies that each block may be composed of a homopolymer or of a copolymer; this copolymer, constituting the block, may in turn be random or alternating.
- The glass transition temperatures indicated for the first and second blocks may be theoretical Tgs determined from the theoretical Tgs of the constituent monomers of each of the blocks, which can be found in a reference manual such as the Polymer Handbook, 3rd ed., 1989, John Wiley, according to the following relationship, called Fox's Law:
- ωi being the mass fraction of the monomer i in the block in question and Tgi being the glass transition temperature of the homopolymer of the monomer i.
- Unless indicated otherwise, the Tgs indicated for the first and second blocks in the present specification are theoretical Tgs.
- The difference between the glass transition temperatures of the first and second blocks is generally greater than 10° C., preferably greater than 20° C. and more preferably greater than 30° C.
- In particular the block polymer comprises at least one first block and at least one second block such that the first block may be selected from:
- a) a block with a Tg of greater than or equal to 40° C.,
- b) a block with a Tg of less than or equal to 20° C.,
- c) a block with a Tg of between 20 and 40° C.,
- and the second block may be selected from a category a), b) or c) different from the first block.
- In the present invention, the expression “between . . . and . . . ” is intended to denote a range of values for which the limits mentioned are excluded, and the expression “from . . . to . . . and “ranging from . . . to . . . ” is intended to denote a range of values for which the limits are included.
- a) Block with a Tg of Greater than or Equal to 40° C.
- The block with a Tg of greater than or equal to 40° C. has, for example, a Tg ranging from 40 to 150° C., preferably greater than or equal to 50° C., ranging for example from 50° C. to 120° C., and better still greater than or equal to 60° C., ranging for example from 60° C. to 120° C.
- The block with a Tg of greater than or equal to 40° C. may be a homopolymer or a copolymer.
- The block with a Tg of greater than or equal to 40° C. may be obtained totally or partly from one or more monomers which are such that the homopolymer prepared from these monomers has a glass transition temperature of greater than or equal to 40° C.
- In the case where this block is a homopolymer, it is obtained from monomers which are such that the homopolymers prepared from these monomers have glass transition temperatures of greater than or equal to 40° C. This first block may be a homopolymer composed of a single type of monomer (for which the Tg of the corresponding homopolymer is greater than or equal to 40° C.).
- In the case where the first block is a copolymer, it may be obtained totally or partly from one or more monomers, the nature and concentration of which are selected such that the Tg of the resulting copolymer is greater than or equal to 40° C. The copolymer may comprise, for example:
- monomers which are such that the homopolymers prepared from these monomers have Tgs of greater than or equal to 40° C., for example a Tg ranging from 40 to 150° C., preferably greater than or equal to 50° C., ranging for example from 50° C. to 120° C., and better still greater than or equal to 60° C., ranging for example from 60° C. to 120° C., and
- monomers which are such that the homopolymers prepared from these monomers have Tgs of less than 40° C., selected from monomers with a Tg of between 20 to 40° C. and/or monomers with a Tg of less than or equal to 20° C., for example a Tg ranging from −100 to 20° C., preferably less than 15° C., especially ranging from −80° C. to 15° C. and better still less than 10° C., for example ranging from −50° C. to 0° C., as described later.
- The monomers whose homopolymers have a glass transition temperature of greater than or equal to 40° C. are selected, preferably, from the following monomers, also known as principal monomers:
- methacrylates of formula CH2═C(CH3)—COOR, in which R1 represents a linear or branched unsubstituted alkyl group containing from 1 to 4 carbon atoms, such as a methyl, ethyl, propyl or isobutyl group, or R1 represents a C4 to C12 cycloalkyl group;
- acrylates of formula CH2═CH—COOR2 in which R2 represents a C4 to C12 cycloalkyl group, such as isobornyl acrylate or a tert-butyl group;
- (meth)acrylamides of formula:
where R7 and R8, which are identical or different, each represent a hydrogen atom or a linear or branched C1 to C12 alkyl group, such as an n-butyl, t-butyl, isopropyl, isohexyl, isooctyl or isononyl group; or R7 represents H and R8 represents a 1,1-dimethyl-3-oxobutyl group and R′ denotes H or methyl. Examples of monomers that may be mentioned include N-butylacrylamide, N-t-butylacrylamide, N-isopropylacrylamide, N,N-dimethylacrylamide and N,N-dibutylacrylamide; - and mixtures thereof.
- Principal monomers that are particularly preferred are methyl methacrylate, isobutyl (meth)acrylate and isobornyl (meth)acrylate, and mixtures thereof.
- b) Block with a Tg of Less than or Equal to 20° C.
- The block with a Tg of less than or equal to 20° C. has, for example, a Tg ranging from −100 to 20° C., preferably less than or equal to 15° C., especially ranging from −80° C. to 15° C. and better still less than or equal to 10° C., for example ranging from −50° C. to 0° C.
- The block with a Tg of less than or equal to 20° C. may be a homopolymer or a copolymer.
- The block with a Tg of less than or equal to 20° C. may be obtained totally or partly from one or more monomers which are such that the homopolymer prepared from these monomers has a glass transition temperature of less than or equal to 20° C.
- In the case where this block is a homopolymer, it is obtained from monomers which are such that the homopolymers prepared from these monomers have glass transition temperatures of less than or equal to 20° C. This second block may be a homopolymer composed of a single type of monomer (for which the Tg of the corresponding homopolymer is less than or equal to 20° C.)
- In the case where the block with a Tg of less than or equal to 20° C. is a copolymer, it may be obtained totally or partly from one or more monomers, the nature and concentration of which are selected such that the Tg of the resulting copolymer is less than or equal to 20° C.
- It may comprise, for example
- one or more monomers whose corresponding homopolymer has a Tg of less than or equal to 20° C., for example a Tg ranging from −100° C. to 20° C., preferably less than 15° C., especially ranging from −80° C. to 15° C. and better still less than 10° C., for example ranging from −50° C. to 0° C., and
- one or more monomers whose corresponding homopolymer has a Tg of greater than 20° C., such as monomers with a Tg of greater than or equal to 40° C., for example a Tg ranging from 40 to 150° C., preferably greater than or equal to 50° C., ranging for example from 50° C. to 120° C. and better still greater than or equal to 60° C., ranging for example from 60° C. to 120° C. and/or monomers with a Tg of between 20 and 40° C., as described above.
- Preferably the block with a Tg of less than or equal to 20° C. is a homopolymer.
- The monomers whose homopolymer has a Tg of less than or equal to 20° C. are selected, preferably, from the following monomers, or principal monomer:
- acrylates of formula CH2═CHCOOR3, R3 representing a linear or branched C1 to C12 unsubstituted alkyl group, with the exception of the tert-butyl group, in which one or more heteroatoms selected from O, N and S is (are) optionally intercalated;
- methacrylates of formula CH2═C(CH3)—COOR4, R4 representing a linear or branched C6 to C12 unsubstituted alkyl group, in which one or more hetero-atoms selected from O, N and S is (are) optionally intercalated;
- vinyl esters of formula R5—CO—O—CH═CH2 where R5 represents a linear or branched C4 to C12 alkyl group;
- C4 to C12 alkyl vinyl ethers;
- N—(C4 to C12 alkyl)acrylamides, such as N-octylacrylamide;
- and mixtures thereof.
- The principal monomers that are particularly preferred for the block with a Tg of less than or equal to 20° C. are alkyl acrylates in which the alkyl chain contains from 1 to 10 carbon atoms, with the exception of the tert-butyl group, such as methyl acrylate, isobutyl acrylate and 2-ethylhexyl acrylate, and mixtures thereof.
- c) Block with a Tg of between 20 and 40° C.
- The block which has a Tg of between 20 and 40° C. may be a homopolymer or a copolymer.
- The block with a Tg of between 20 and 40° C. may be obtained totally or partly from one or more monomers which are such that the homopolymer prepared from these monomers has a glass transition temperature of between 20 and 40° C.
- The block with a Tg of between 20 and 40° C. may be obtained totally or partly from monomers which are such that the corresponding homopolymer has a Tg of greater than or equal to 40° C. and from monomers which are such that the corresponding homopolymer has a Tg of less than or equal to 20° C.
- In the case where this block is a homopolymer, it is obtained from monomers (or principal monomers) which are such that the homopolymers prepared from these monomers have glass transition temperatures of between 20 and 40° C. This first block may be a homopolymer composed of a single type of monomer (for which the Tg of the corresponding homopolymer ranges from 20° C. to 40° C.).
- The monomers whose homopolymer has a glass transition temperature of between 20 and 40° C. are selected, preferably, from n-butyl methacrylate, cyclodecyl acrylate, neopentyl acrylate and isodecylacrylamide, and mixtures thereof.
- In the case where the block with a Tg of between 20 and 40° C. is a copolymer, it is obtained totally or partly from one or more monomers (or principal monomers) the nature and concentration of which are selected such that the Tg of the resulting copolymer is between 20 and 40° C.
- Advantageously the block with a Tg of between 20 and 40° C. is a copolymer obtained totally or partly from:
- principal monomers whose corresponding homopolymer has a Tg of greater than or equal to 40° C., for example a Tg ranging from 40° C. to 150° C., preferably greater than or equal to 50° C., ranging for example from 50 to 120° C. and better still greater than or equal to 60° C., ranging for example from 60° C. to 120° C., as described above; and/or
- principal monomers whose corresponding homopolymer has a Tg of less than or equal to 20° C., for example a Tg ranging from −100 to 20° C., preferably less than or equal to 15° C., especially ranging from −80° C. to 15° C. and better still less than or equal to 10° C., for example ranging from −50° C. to 0° C., as described above, the said monomers being selected such that the Tg of the copolymer forming the first block is between 20 and 40° C.
- Such principal monomers are selected, for example, from methyl methacrylate, isobornyl acrylate and methacrylate, butyl acrylate and 2-ethylhexyl acrylate, and mixtures thereof.
- Preferably the proportion of the second block with a Tg of less than or equal to 20° C. ranges from 10% to 85%, better still from 20% to 70% and even better still from 20% to 50% by weight of the polymer.
- Preferably each of the first and second blocks comprises at least one monomer selected from acrylic acid, the esters of acrylic acid, (meth)acrylic acid, the esters of (meth)acrylic acid, and mixtures thereof.
- Advantageously each of the first and second blocks is obtained totally from at least one monomer selected from acrylic acid, the esters of acrylic acid, (meth)acrylic acid, the esters of (meth)acrylic acid, and mixtures thereof.
- However, each of the blocks may contain in minority proportion at least one constituent monomer of the other block.
- Thus the first block may contain at least one constituent monomer of the second block, and vice versa.
- Each of the first and/or second blocks may comprise, in addition to the monomers indicated above, one or more other monomers known as additional monomers, which are different from the principal monomers mentioned above.
- The nature and amount of this or these additional monomer(s) are selected such that the block in which they are present has the desired glass transition temperature.
- This additional monomer is selected, for example, from:
- a) hydrophilic monomers such as:
- ethylenically unsaturated monomers comprising at least one carboxylic or sulphonic acid function, for instance: acrylic acid, methacrylic acid, crotonic acid, maleic anhydride, itaconic acid, fumaric acid, maleic acid, acrylamidopropanesulphonic acid, vinylbenzoic acid, vinylphosphoric acid, and salts thereof;
- ethylenically unsaturated monomers comprising at least one tertiary amine function, for instance 2-vinylpyridine, 4-vinylpyridine, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate and dimethylaminopropylmethacrylamide, and salts thereof;
- methacrylates of formula CH2═C(CH3)—COOR6 in which R6 represents a linear or branched alkyl group containing from 1 to 4 carbon atoms, such as a methyl, ethyl, propyl or isobutyl group, the said alkyl group being substituted by one or more substituents selected from hydroxyl groups (for instance 2-hydroxypropyl methacrylate and 2-hydroxyethyl methacrylate) and halogen atoms (Cl, Br, I or F), such as trifluoroethyl methacrylate;
- methacrylates of formula CH2═C(CH3)—COOR9, R9 representing a linear or branched C6 to C12 alkyl group in which one or more heteroatoms selected from O, N and S is (are) optionally intercalated, the said alkyl group being substituted by one or more substituents selected from hydroxyl groups and halogen atoms (Cl, Br, I or F);
- acrylates of formula CH2═CHCOOR10, R10 representing a linear or branched C1 to C12 alkyl group substituted by one or more substituents selected from hydroxyl groups and halogen atoms (Cl, Br, I or F), such as 2-hydroxypropyl acrylate and 2-hydroxyethyl acrylate, or R10 represents a C1 to C12 alkyl-O-POE (polyoxyethylene) with repetition of the oxyethylene unit from 5 to 30 times, for example methoxy-POE, or R10 represents a polyoxyethylenated group comprising from 5 to 30 ethylene oxide units;
- b) ethylenically unsaturated monomers comprising one or more silicon atoms, such as methacryloxypropyltrimethoxysilane and methacryloxypropyltris(trimethylsiloxy)silane;
- and mixtures thereof.
- Additional monomers that are particularly preferred are acrylic acid, methacrylic acid and trifluoroethyl methacrylate, and mixtures thereof.
- According to one embodiment, each of the first and second blocks of the block polymer comprises at least one monomer selected from esters of (meth)acrylic acid and optionally at least one additional monomer such as (meth)acrylic acid, and mixtures thereof.
- According to another embodiment, each of the first and second blocks of the block polymer is obtained totally from at least one monomer selected from esters of (meth)acrylic acid and optionally at least one additional monomer such as (meth)acrylic acid, and mixtures thereof.
- According to one preferred embodiment, the block polymer is a non-silicone polymer, i.e. a polymer free of silicon atoms.
- This or these additional monomer(s) generally represent(s) an amount of less than or equal to 30% by weight, for example from 1% to 30% by weight, preferably from 5% to 20% by weight and more preferably from 7% to 15% by weight, relative to the total weight of the first and/or second blocks.
- The block polymer may be obtained by free-radical solution polymerization according to the following preparation process:
- a portion of the polymerization solvent is introduced into a suitable reactor and heated until the adequate temperature for the polymerization is reached (typically between 60 and 120° C.),
- once this temperature is reached, the constituent monomers of the first block are introduced in the presence of a portion of the polymerization initiator,
- after a time T corresponding to a maximum degree of conversion of 90%, the constituent monomers of the second block and the rest of the initiator are introduced,
- the mixture is left to react for a time T′ (ranging from 3 to 6 hours), after which the mixture is cooled to ambient temperature,
- the polymer in solution in the polymerization solvent is obtained.
- According to a first embodiment, the block polymer comprises a first block with a Tg of greater than or equal to 40° C., as described above in a), and a second block with a Tg of less than or equal to 20° C., as described above in b).
- Preferably the first block with a Tg of greater than or equal to 40° C. is a copolymer obtained from monomers which are such that the homopolymer prepared from these monomers has a glass transition temperature of greater than or equal to 40° C., such as the monomers described above.
- Advantageously the second block with a Tg of less than or equal to 20° C. is a homopolymer obtained from monomers which are such that the homopolymer prepared from these monomers has a glass transition temperature of less than or equal to 20° C., such as the monomers described above.
- Preferably the proportion of the block with a Tg of greater than or equal to 40° C. ranges from 20% to 90%, better still from 30% to 80% and even better still from 50% to 70% by weight of the polymer.
- Preferably the proportion of the block with a Tg of less than or equal to 20° C. ranges from 5% to 75%, preferably from 15% to 50% and better still from 25% to 45% by weight of the polymer.
- Thus, according to a first variant, the polymer according to the invention may comprise:
- a first block with a Tg of greater than or equal to 40° C., for example having a Tg ranging from 70 to 110° C., which is a methyl methacrylate/acrylic acid copolymer,
- a second block with a Tg of less than or equal to 20° C., for example ranging from 0 to 20° C., which is a methyl acrylate homopolymer, and
- an intermediate block which is a methyl methacrylate/acrylic acid/methyl acrylate copolymer.
- According to a second variant, the polymer according to the invention may comprise:
- a first block with a Tg of greater than or equal to 40° C., for example ranging from 70 to 100° C., which is a methyl methacrylate/acrylic acid/trifluoroethyl methacrylate copolymer,
- a second block with a Tg of less than or equal to 20° C., for example ranging from 0 to 20° C., which is a methyl acrylate homopolymer, and
- an intermediate block which is a methyl methacrylate/acrylic acid/methyl acrylate/trifluoro-ethyl methacrylate random copolymer.
- According to a third variant, the polymer according to the invention may comprise:
- a first block with a Tg of greater than or equal to 40° C., for example ranging from 85 to 115° C., which is an isobornyl acrylate/isobutyl methacrylate copolymer,
- a second block with a Tg of less than or equal to 20° C., for example ranging from −85 to −55° C., which is a 2-ethylhexyl acrylate homopolymer, and
- an intermediate block which is an isobornyl acrylate/isobutyl methacrylate/2-ethylhexyl acrylate random copolymer.
- According to a fourth variant, the polymer according to the invention may comprise:
- a first block with a Tg of greater than or equal to 40° C., for example ranging from 85 to 115° C., which is an isobornyl acrylate/methyl methacrylate copolymer,
- a second block with a Tg of less than or equal to 20° C., for example ranging from −85 to −55° C., which is a 2-ethylhexyl acrylate homopolymer, and
- an intermediate block which is an isobornyl acrylate/methyl methacrylate/2-ethylhexyl acrylate random copolymer.
- According to a fifth variant, the polymer according to the invention may comprise:
- a first block with a Tg of greater than or equal to 40° C., for example ranging from 95 to 125° C., which is an isobornyl acrylate/isobornyl methacrylate copolymer,
- a second block with a Tg of less than or equal to 20° C., for example ranging from −85 to −55° C., which is a 2-ethylhexyl acrylate homopolymer, and
- an intermediate block which is an isobornyl acrylate/isobornyl methacrylate/2-ethylhexyl acrylate random copolymer.
- According to a sixth variant, the polymer according to the invention may comprise:
- a first block with a Tg of greater than or equal to 40° C., for example ranging from 85 to 115° C., which is an isobornyl methacrylate/isobutyl methacrylate copolymer,
- a second block with a Tg of less than or equal to 20° C., for example ranging from −35 to −5° C., which is an isobutyl acrylate homopolymer, and
- an intermediate block which is an isobornyl methacrylate/isobutyl methacrylate/isobutyl acrylate random copolymer.
- According to a seventh variant, the polymer according to the invention may comprise:
- a first block with a Tg of greater than or equal to 40° C., for example ranging from 95 to 125° C., which is an isobornyl acrylate/isobornyl methacrylate copolymer,
- a second block with a Tg of less than or equal to 20° C., for example ranging from −35 to −5° C., which is an isobutyl acrylate homopolymer, and
- an intermediate block which is an isobornyl acrylate/isobornyl methacrylate/isobutyl acrylate random copolymer.
- According to an eighth variant, the polymer according to the invention may comprise:
- a first block with a Tg of greater than or equal to 40° C., for example ranging from 60 to 90° C., which is an isobornyl acrylate/isobutyl methacrylate copolymer,
- a second block with a Tg of less than or equal to 20° C., for example ranging from −35 to −5° C., which is an isobutyl acrylate homopolymer, and
- an intermediate block which is an isobornyl acrylate/isobutyl methacrylate/isobutyl acrylate random copolymer.
- The examples which follow illustrate, non-limitatively, polymers corresponding to this first embodiment.
- The amounts are expressed in grams.
- 100 g of butyl acetate are introduced into a 1 litre reactor and then the temperature is raised so as to go from ambient temperature (25° C.) to 90° C. over 1 hour.
- Subsequently there are added, at 90° C. and over 1 hour, 180 g of methyl methacrylate, 30 g of acrylic acid, 40 g of butyl acetate, 70 g of isopropanol and 1.8 g of 2,5-bis(2-ethylhexanoyl-peroxy)-2,5-dimethylhexane (Trigonox® 141 from Akzo Nobel).
- The mixture is held at 90° C. for 1 hour.
- Subsequently there are introduced into the above mixture, still at 90° C. and over 1 hour, 90 g of methyl acrylate, 70 g of butyl acetate, 20 g of isopropanol and 1.2 g of 2,5-bis(2-ethylhexanoyl-peroxy)-2,5-dimethylhexane.
- The mixture is held at 90° C. for 3 hours, then diluted in 105 g of butyl acetate and 45 g of isopropanol, and then the whole is cooled.
- This gives a solution containing 40% polymer active substance in the butyl acetate/isopropanol mixture.
- A polymer is obtained which comprises a first, poly(methyl methacrylate/acrylic acid) block with a Tg of 100° C., a second, polymethyl acrylate block with a Tg of 10° C., and an intermediate block which is a methyl methacrylate/acrylic acid/polymethyl acrylate random polymer.
- This polymer has a weight-average mass of 52 000 and a number-average mass of 18 000, giving a polydispersity index I of 2.89.
- 100 g of isododecane are introduced into a 1 litre reactor and then the temperature is raised so as to go from ambient temperature (25° C.) to 90° C. over 1 hour.
- Subsequently there are added, at 90° C. and over 1 hour, 120 g of isobornyl acrylate, 90 g of isobutyl methacrylate, 110 g of isododecane and 1.8 g of 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane (Trigonox® 141 from Akzo Nobel).
- The mixture is held at 90° C. for 1.5 h.
- Subsequently there are introduced into the above mixture, still at 90° C. and over 30 minutes, 90 g of 2-ethylhexyl acrylate, 90 g of isododecane and 1.2 g of 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane.
- The mixture is held at 90° C. for 3 hours and then the whole is cooled.
- This gives a solution containing 50% polymer active substance in isododecane.
- A polymer is obtained which comprises a first, poly(isobornyl acrylate/isobutyl methacrylate) block with a Tg of 80° C., a second, poly-2-ethylhexyl acrylate block with a Tg of −70° C., and an intermediate block which is an isobornyl acrylate/isobutyl methacrylate/2-ethylhexyl acrylate random polymer.
- This polymer has a weight-average mass of 77 000 and a number-average mass of 19 000, giving a polydispersity index I of 4.05.
- 100 g of isododecane are introduced into a 1 litre reactor and then the temperature is raised so as to go from ambient temperature (25° C.) to 90° C. over 1 hour.
- Subsequently there are added, at 90° C. and over 1 hour, 150 g of isobornyl acrylate, 60 g of methyl methacrylate, 110 g of isododecane and 1.8 g of 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane (Trigonox® 141 from Akzo Nobel).
- The mixture is held at 90° C. for 1.5 h.
- Subsequently there are introduced into the above mixture, still at 90° C. and over 30 minutes, 90 g of 2-ethylhexyl acrylate, 90 g of isododecane and 1.2 g of 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane.
- The mixture is held at 90° C. for 3 hours and then the whole is cooled.
- This gives a solution containing 50% polymer active substance in isododecane.
- A polymer is obtained which comprises a first, poly(isobornyl acrylate/methyl methacrylate) block with a Tg of 100° C., a second, poly-2-ethylhexyl acrylate block with a Tg of −70° C., and an intermediate block which is an isobornyl acrylate/methyl methacrylate/2-ethylhexyl acrylate random polymer.
- This polymer has a weight-average mass of 76 500 and a number-average mass of 22 000, giving a polydispersity index I of 3.48.
- 100 g of isododecane are introduced into a 1 litre reactor and then the temperature is raised so as to go from ambient temperature (25° C.) to 90° C. over 1 hour.
- Subsequently there are added, at 90° C. and over 1 hour, 105 g of isobornyl acrylate, 105 g of isobornyl methacrylate, 110 g of isododecane and 1.8 g of 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane (Trigonox® 141 from Akzo Nobel).
- The mixture is held at 90° C. for 1.5 h.
- Subsequently there are introduced into the above mixture, still at 90° C. and over 30 minutes, 90 g of 2-ethylhexyl acrylate, 90 g of isododecane and 1.2 g of 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane.
- The mixture is held at 90° C. for 3 hours and then the whole is cooled.
- This gives a solution containing 50% polymer active substance in isododecane.
- A polymer is obtained which comprises a first, poly(isobornyl acrylate/isobornyl methacrylate) block or sequence with a Tg of 110° C., a second, poly-2-ethylhexyl acrylate block with a Tg of −70° C., and an intermediate block which is an isobornyl acrylate/isobornyl methacrylate/2-ethylhexyl acrylate random polymer.
- This polymer has a weight-average mass of 103 900 and a number-average mass of 21 300, giving a polydispersity index I of 4.89.
- According to a second embodiment, the block polymer comprises a first block with a glass transition temperature (Tg) of between 20 and 40° C., in accordance with the blocks described in c), and a second block with a glass transition temperature of less than or equal to 20° C., as described above in b), or a glass transition temperature of greater than or equal to 40° C., as described in a) above.
- Preferably the proportion of the first block with a Tg of between 20 and 40° C. ranges from 10% to 85%, better still from 30% to 80% and even better still from 50% to 70% by weight of the polymer.
- When the second block is a block with a Tg of greater than or equal to 40° C., it is preferably present in a proportion ranging from 10% to 85% by weight, better still from 20% to 70% and even better still from 30% to 70% by weight of the polymer.
- When the second block is a block with a Tg of less than or equal to 20° C., it is preferably present in a proportion ranging from 10% to 85% by weight, better still from 20% to 70% and even better still from 20% to 50% by weight of the polymer.
- Preferably the first block with a Tg of between 20 and 40° C. is a copolymer obtained from monomers which are such that the corresponding homopolymer has a Tg of greater than or equal to 40° C., and from monomers which are such that the corresponding homopolymer has a Tg of less than or equal to 20° C.
- Advantageously the second block with a Tg of less than or equal to 20° C. or with a Tg of greater than or equal to 40° C. is a homopolymer.
- Thus, according to a first variant of this second embodiment, the block polymer may comprise:
- a first block with a Tg of between 20 and 40° C., for example with a Tg of 25 to 39° C., which is a copolymer comprising at least one methyl acrylate monomer, at least one methyl methacrylate monomer and at least one acrylic acid monomer,
- a second block with a Tg of greater than or equal to 40° C., for example ranging from 85 to 125° C., which is a homopolymer composed of methyl methacrylate monomers, and
- an intermediate block comprising at least one methyl acrylate or methyl methacrylate monomer, and
- an intermediate block comprising methyl methacrylate, at least one acrylic acid monomer and at least one methyl acrylate monomer.
- According to a second variant of this second embodiment, the block polymer may comprise:
- a first block with a Tg of between 20 and 40° C., for example with a Tg of 21 to 39° C., which is a copolymer comprising isobornyl acrylate/isobutyl methacrylate/2-ethylhexyl acrylate,
- a second block with a Tg of less than or equal to 20° C., for example ranging from −65 to −35° C., which is a methyl methacrylate homopolymer, and
- an intermediate block which is an isobornyl acrylate/isobutyl methacrylate/2-ethylhexyl acrylate random copolymer.
- According to a third variant of this second embodiment, the block polymer may comprise:
- a first block with a Tg of between 20 and 40° C., for example with a Tg of from 21 to 39° C., which is an isobornyl acrylate/methyl acrylate/acrylic acid copolymer,
- a second block with a Tg of greater than or equal to 40° C., for example ranging from 85 to 115° C., which is an isobornyl acrylate homopolymer, and
- an intermediate block which is an isobornyl acrylate/methyl acrylate/acrylic acid random copolymer.
- By way of illustration, but without limitation, the polymers corresponding to this second embodiment may be realised as follows.
- 100 g of butyl acetate are introduced into a 1 litre reactor and then the temperature is raised so as to go from ambient temperature (25° C.) to 90° C. over 1 hour.
- Subsequently there are added, at 90° C. and over 1 hour, 50.4 g of methyl methacrylate, 21 g of acrylic acid, 138.6 g of methyl acrylate, 40 g of butyl acetate, 70 g of isopropanol and 1.8 g of 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane (Trigonox® 141 from Akzo Nobel).
- The mixture is held at 90° C. for 1 hour.
- Subsequently there are introduced into the above mixture, still at 90° C. and over 1 hour, 90 g of methyl methacrylate, 70 g of butyl acetate, 20 g of isopropanol and 1.2 g of 2,5-bis(2-ethylhexanoyl-peroxy)-2,5-dimethylhexane.
- The mixture is held at 90° C. for 3 hours and then diluted with 105 g of butyl acetate and 45 g of isopropanol, and the whole is then cooled.
- This gives a solution containing 40% polymer active substance in the butyl acetate/isopropanol mixture.
- The polymer obtained comprises a first poly(methyl acrylate/methyl methacrylate/acrylic acid) block having a Tg of 35° C., a second poly(methyl methacrylate) block having a Tg of 100° C. and an intermediate block which is a methyl methacrylate/acrylic acid/polymethyl acrylate random polymer.
- 100 g of isododecane are introduced into a 1 litre reactor and then the temperature is raised so as to go from ambient temperature (25° C.) to 90° C. over 1 hour.
- Subsequently there are added, at 90° C. and over 1 hour, 54 g of isobornyl acrylate, 75.6 g of isobutyl methacrylate, 50.4 g of 2-ethylhexyl acrylate, 110 g of isododecane and 1.8 g of 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane (Trigonox® 141 from Akzo Nobel).
- The mixture is held at 90° C. for 1.5 h.
- Subsequently there are introduced into the above mixture, still at 90° C. and over 1 hour, 120 g of 2-ethylhexyl acrylate, 90 g of isododecane and 1.2 g of 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane.
- The mixture is held at 90° C. for 3 hours and then diluted and the whole is then cooled.
- This gives a solution containing 50% of polymer active substance in isododecane.
- A polymer is obtained which comprises a first poly(isobornyl acrylate/isobutyl methacrylate/2-ethyl-hexyl acrylate) block having a Tg of 25° C., a second poly-2-ethylhexyl acrylate block having a Tg of −50° C. and an intermediate block which is an isobornyl acrylate/isobutyl methacrylate/2-ethylhexyl acrylate random polymer.
- The composition according to the invention contains preferably from 0.1% to 60% by weight of active substance (or solids) of the polymer, preferably from 0.5% to 50% by weight and more preferably from 1% to 40% by weight.
- Gelling Agent
- The composition of the invention also comprises at least one agent for gelling the organic liquid medium of the composition. The gelling agent may increase the viscosity of the organic liquid medium and may lead to a solid or flowable composition when introduced into the said organic liquid medium.
- The gelling agent may be selected from gelling agents in polymeric form and gelling agents in mineral form.
- In one embodiment the gelling agent is not soluble in an aqueous phase or in water.
- The gelling agent according to the present invention is selected preferably from the group consisting of agents which gel via chemical crosslinking and agents which gel via physical crosslinking.
- Gelling Agents which Gel Via Chemical Crosslinking
- According to one embodiment, preference is given to crosslinked elastomeric polyorganosiloxanes of three-dimensional structure, such as MQ silicone resins, polyalkylsesquioxanes, especially polymethyl-sesquioxanes, and resins crosslinked via hydro-silylation. These silicone resins may carry hydrophilic groups, such as polyoxyethylene or copoly(oxyethylene/oxypropylene).
- As polyorganosiloxanes which can be used in the invention, mention may be made of the crosslinked elastomeric polyorganosiloxanes described in application EP-A-0 295 886, the disclosure of which is incorporated in this text by reference. According to that application they are obtained by addition reaction and crosslinking, in the presence of a platinum-type catalyst, of at least:
- (a) a polyorganosiloxane having at least two C2 to C6 lower alkenyl groups per molecule; and
- (b) a polyorganosiloxane having at least two hydrogen atoms bonded to a silicon atom per molecule. It is also possible to use the polyorganosiloxanes described in U.S. Pat. No. 5,266,321, the disclosure of which is incorporated in this text by reference. According to that patent they are selected in particular from:
- i) polyorganosiloxanes comprising R2SiO and RSiO1.5 units and optionally R3SiO0.5 and/or SiO2 units, in which the radicals R1, independently of one another, are selected from a hydrogen, an alkyl such as methyl, ethyl or propyl, an aryl such as phenyl or tolyl, an unsaturated aliphatic group such as vinyl, the weight ratio of the units R2SiO to the units RSiO1.5 ranging from 1/1 to 30/1;
- ii) polyorganosiloxanes which are insoluble and swellable in silicone oil, obtained by addition of a polyorganohydrosiloxane (1) and a polyorganosiloxane (2) having unsaturated aliphatic groups such that the amount of hydrogen or of unsaturated aliphatic groups in (1) and (2) respectively ranges from 1 to 20 mol % when the polyorganosiloxane is non-cyclic and from 1 to 50 mol % when the polyorganosiloxane is cyclic. Optionally these polyorganosiloxanes can comprise from 1 to 40 oxyalkylene groups, such as oxypropylene and/or oxyethylene groups.
- As examples of polyorganosiloxanes which can be used according to the invention, mention may be made of those sold or made under the names KSG6 from Shin-Etsu, Trefil E-505C or Trefil E-506C from Dow Corning, Gransil from Grant Industries (SR-CYC, SR DMF10, SR-DC556) or those sold in the form of preconstituted gels (KSG15, KSG17, KSG16, KSG18 and KSG21 from Shin-Etsu, Gransil SR SCYC gel, Gransil SR DMF 10 gel, Gransil SR DC556 gel, SF 1204 and JK 113 from General Electric. A mixture of these commercial products may also be used.
- Gelling Agents which Gel Via Physical Crosslinking
- Gelling agents which gel via physical crosslinking, particularly by molecular agitation, hydrogen interactions or dipolar interactions, and also fat-soluble polymers having liquid crystal groups, are preferred.
- Gelling agents which gel via molecular agitation are polymers having high molecular weights, preferably greater than 500 000, such as silicone gums.
-
- R7, R8, R11 and R12 are identical or different and each is selected from alkyl radicals containing from 1 to 6 carbon atoms,
- R9 and R10 are identical or different and each is selected from alkyl radicals containing from 1 to 6 carbon atoms and aryl radicals,
- X is selected from alkyl radicals containing from 1 to 6 carbon atoms, a hydroxyl radical and a vinyl radical, n and p are selected so as to give the silicone gum a viscosity of greater than 100 000 mPa·s, such as greater than 500 000 mPa·s.
In general, n and p can each take values ranging from 0 to 5000, such as from 0 to 3000. - Among the silicone gums which can be used as a gelling agent according to the invention, mention may be made of those for which:
- the substituents R7 to R12 and X represent a methyl group, p=0 and n=2700, such as the product sold or made under the name SE30 by the company General Electric,
- the substituents R7 to R12 and X represent a methyl group, p=0 and n=2300, such as the product sold or made under the name AK 500 000 by the company Wacker,
- the substituents R7 to R12 represent a methyl group, the substituent X represents a hydroxyl group, p=0 and n=2700, in the form of a 13% solution in cyclopentasiloxane, such as the product sold or made under the name Q2-1401 by the company Dow Corning,
- the substituents R7 to R12 represent a methyl group, the substituent X represents a hydroxyl group, p=0 and n=2700, in the form of 13% solution in polydimethylsiloxane, such as the product sold or made under the name Q2-1403 by the company Dow Corning, and
- the substituents R7, R8, R11, R12 and X represent a methyl group and the substituents R9 and R10 represent an aryl group, such that the molecular weight of the gum is approximately 600 000, for example the product sold or made under the name 761 by the company Rhöne-Poulenc (Rhodia Chimie).
- Gelling agents which gel the organic liquid medium via hydrogen interactions are selected preferably from the group consisting of:
- aminosilicone polymers having triazinyl groups or pyrimidinyl groups bonded to amino groups of aminosilicones, as described in patent application EP 0 751 170, the disclosure of which is incorporated in this text by reference,
- non-silicone polyamides whose ends carry ester or triamide functions, such as the compounds described in patents and patent applications U.S. Pat. No. 5,783,657, U.S. Pat. No. 6,268,466, WO 01/95871, WO 00/40216, U.S. Pat. No. 2002/0035237 and EP 1 068 856, the disclosure of which is incorporated in this text by reference,
- polyurethanes, such as the compounds described in patent applications DE 100 22 247 and FR 2 814 365, the disclosure of which is incorporated in this text by reference, and
- vinyl and/or (meth)acrylic polymers carrying side groups which are able to give rise to mutual hydrogen interactions, such as the compounds described in patent application WO 93/01797, the disclosure of which is incorporated in this text by reference.
- Gelling agents may also be selected from the group consisting of:
- copolymers such as polystyrene-silicone or polyethylene-silicone, described in patents U.S. Pat. No. 6,225,390, U.S. Pat. No. 6,160,054, U.S. Pat. No. 6,174,968 and U.S. Pat. No. 6,225,390, the disclosures of which are incorporated in this text by reference,
- copolymers comprising a silicone block and another block or graft which is polyvinylic or poly(meth)acrylic, such as those described in patents U.S. Pat. No. 5,468,477 and U.S. Pat. No. 5,725,882, the disclosures of which are incorporated in this text by reference,
- polymers or copolymers resulting from the polymerization or copolymerization of an ethylenic monomer containing one or more ethylenic, preferably conjugated, bonds (or dienes),
- polymers or copolymers resulting from the polymerization or copolymerization of an ethylenic monomer; in particular it is possible to use vinyl, acrylic or methacrylic copolymers. The ethylenic gelling agent may comprise, for example, a styrene (S) block and an alkylstyrene (AS) block, and a block selected from ethylene/butylene (EB), ethylene/propylene (EP), butadiene (B), isoprene (I), acrylate (A) and methacrylate (MA) blocks or a combination of these blocks.
- In one embodiment a copolymer comprising at least one styrene block is used as gelling agent. A triblock copolymer, and in particular those of the polystyrene/polyisoprene or polystyrene/polybutadiene type, such as those sold or made under the name “Luvitol HSB” by BASF and those of the polystyrene/copoly(ethylene-propylene) type or, alternatively, those of the polystyrene/copoly(ethylene/butylene) type, such as those sold or made under the brand name “Kraton” by Shell Chemical Co. or Gelled Permethyl 99A by Penreco, may be used. Styrene-methacrylate copolymers may also be used.
- As an ethylenic gelling agent which can be used in the composition of the invention, mention may be made, for example, of Kraton G1650 (SEBS), Kraton G1651 (SEBS), Kraton G1652 (SEBS), Kraton G1657X (SEBS), Kraton G1701X (SEP), Kraton G1702X (SEP), Kraton G1726X (SEB), Kraton D-1101 (SBS), Kraton D-1102 (SBS), Kraton D-1107 (SIS), Gelled Permethyl 99A-750, Gelled Permethyl 99A-753-58, Gelled Permethyl 99A-753-59, Versagel 5970 and Versagel 5960 from Penreco, and OS 129880, OS 129881 and OS 84383 from Lubrizol (styrene-methacrylate copolymer).
- Diblocks or triblocks such as polystyrene-copoly(ethylene/propylene) or polystyrene-copoly(ethylene/butylene), such as those described in patent applications WO 98/38981 and US 2002/0055562 are also included in the present invention.
- Gelling agents which gel via dipolar interactions are selected preferably from the compounds described in documents WO 01/30886 and U.S. Pat. No. 6,228,967, the disclosures of which are incorporated in this text by reference. The ionized groups in the said compounds, for example the zwitterionic groups, create the said dipolar interactions.
- Gelling agents such as the fat-soluble polymers having liquid crystal groups are also preferred according to the present invention, particularly fat-soluble polymers whose skeleton is of silicone, vinyl and/or (meth)acrylic type, and which possess liquid crystal side groups, especially the compounds described in patent application FR 2 816 503, the disclosure of which is incorporated in this text by reference.
- In another embodiment the gelling agent may be in mineral form.
- The gelling agent may be a modified clay. As modified clays which can be used, mention may be made of hectorites modified with an ammonium chloride of a C10 to C22 fatty acid, such as a hectorite modified with distearyldimethylammonium chloride, also known as bentonite of quaternium-18, such as the products sold or made under the names Bentone 34 by the company Rheox, Claytone XL, Claytone 34 and Claytone 40 sold or made by the company Southern Clay, modified clays known under the name quaternium-18 bentonites and benzalkonium bentonites and sold or made under the names Claytone HT, Claytone GR and Claytone PS by the company Southern Clay, clays modified with stearyldimethylbenzoylammonium chloride, known as stearalkonium bentonites, such as the products sold or made under the names Claytone APA and Claytone AF by the company Southern Clay, and Baragel 24, sold or made by the company Rheox.
- As other mineral gelling agents which can be used in the invention, mention may be made of silica, such as fumed silica. The fumed silica may have a particle size which may be nanometric or micrometric, for example ranging from approximately 5 nm to 200 nm.
- Fumed silicas may be obtained by high-temperature hydrolysis of a volatile silicon compound in an oxyhydrogen flame, producing a finely divided silica. This process allows hydrophilic silicas to be obtained which possess a large number of silanol groups on their surface. The silanol groups may be replaced, for example, by hydrophobic groups: this then gives a hydrophobic silica. The hydrophobic groups may be:
- trimethylsiloxyl groups, which are obtained in particular by treating fumed silica in the presence of hexamethyldisilazane. The silicas thus treated are known as “silica silylate” according to the CTFA (6th edition, 1995). They are sold or made, for example, under the references “Aerosil R812®” by the company Degussa, and “CAB-O-SIL TS-530® by the company Cabot;
- dimethylsilyloxyl or polydimethylsiloxane groups, which are obtained in particular by treating fumed silica in the presence of polydimethyldisiloxane or dimethyldichlorosilane. The silicas thus treated are known as “silica dimethylsilylate” according to the CTFA (6th edition, 1995). They are sold or made, for example, under the references “Aerosil R972®” and “Aerosil R974®” by the company Degussa, and “CAB-O-SIL TS-610®” and “CAB-O-SIL TS-720®” by the company Cabot;
- groups derived from the reaction of fumed silica with silane alkylates or siloxanes. These treated silicas are, for example, the products sold or made under the reference “Aerosil R805®” by the company Degussa.
- According to the invention a hydrophobic silica, such as a fumed silica, may be used as gelling agent.
- The gelling agent may be used, for example, in concentrations ranging from 0.05% to 35% of the total weight of the composition, for example from 0.5% to 20% or from 1% to 10%.
- The composition according to the invention may comprise a hydrophilic medium comprising water or a mixture of water and hydrophilic organic solvent(s) such as alcohols and especially linear or branched lower monoalcohols having from 2 to 5 carbon atoms such as ethanol, isopropanol or n-propanol, and polyols such as glycerol, diglycerol, propylene glycol, sorbitol, pentylene glycol, and polyethylene glycols, or else C2 ethers and C2-C4 aldehydes which are hydrophilic.
- The water or the mixture of water and hydrophilic organic solvents may be present in the composition according to the invention in an amount ranging from 0.1% to 99% by weight, relative to the total weight of the composition, and preferably from 10% to 80% by weight.
- The composition according to the invention comprises an organic liquid medium which is cosmetically acceptable (acceptable tolerance, toxicology and feel).
- According to one particularly preferred embodiment the organic liquid medium of the composition comprises at least one organic solvent, which is the, or one of the, polymerization solvent(s) of the block polymer as described above. Advantageously the said organic solvent is the majority liquid by weight in the organic liquid medium of the cosmetic composition.
- According to one embodiment, the organic liquid medium comprises fatty substances which are liquid at ambient temperature (25° C. in general). These liquid fatty substances may be animal, vegetable, mineral or synthetic in origin.
- As fatty substances which are liquid at ambient temperature, often called oils, which can be used in the invention mention may be made of: hydrocarbon oils of animal origin, such as perhydrosqualene; vegetable hydrocarbon oils, such as liquid triglycerides of fatty acids of 4 to 10 carbon atoms, such as heptanoic or octanoic acid triglycerides, or else sunflower oil, corn oil, soya oil, grape seed oil, sesame oil, apricot oil, macadamia oil, castor oil, avocado oil, caprylic/capric acid triglycerides, jojoba oil, karite butter; linear or branched hydrocarbons, of mineral or synthetic origin, such as liquid paraffins and derivatives thereof, Vaseline, polydecenes, hydrogenated polyisobutene such as parleam; the synthetic esters and ethers particularly of fatty acids, such as, for example, purcellin oil, isopropyl myristate, 2-ethylhexyl palmitate, 2-octyldodecyl stearate, 2-octyldodecyl erucate, isostearyl isostearate; hydroxylated esters such as isostearyl lactate, octyl hydroxystearate, octyldodecyl hydroxystearate, diisostearyl malate, triisocetyl citrate, and heptanoates, octanoates and decanoates of fatty alcohols; polyol esters such as propylene glycol dioctanoate, neopentyl glycol diheptanoate and diethylene glycol diisononanoate; and pentaerythritol esters; fatty alcohols having 12 to 26 carbon atoms, such as octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol, and oleyl alcohol; partially hydrocarbon-based and/or silicone-based fluoro oils; silicone oils, such as volatile or non-volatile polydimethylsiloxanes (PDMS) that are linear or cyclic, such as cyclomethicones, dimethicones, optionally including a phenyl group, such as phenyl trimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenylmethyldimethyltrisiloxanes, diphenyldimethicones, phenyldimethicones and polymethylphenylsiloxanes; and mixtures thereof.
- These oils may be present in an amount ranging from 0.01% to 90%, and better still from 0.1% to 85% by weight, relative to the total weight of the composition.
- The organic liquid medium of the composition according to the invention may also comprise one or more organic solvents which are cosmetically acceptable (acceptable tolerance, toxicology and feel).
- These solvents may be generally present in an amount ranging from 0.1% to 90%, more preferably from 10% to 90% by weight, relative to the total weight of the composition, and better still from 30% to 90%.
- As solvents which can be used in the composition of the invention mention may be made, besides the aforementioned hydrophilic organic solvents, of ketones which are liquid at ambient temperature, such as methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, isophorone, cyclohexanone and acetone; propylene glycol ethers which are liquid at ambient temperature, such as propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and dipropylene glycol mono-n-butyl ether; short-chain esters (having 3 to 8 carbon atoms in total), such as ethyl acetate, methyl acetate, propyl acetate, n-butyl acetate and isopentyl acetate; ethers which are liquid at ambient temperature, such as diethyl ether, dimethyl ether or dichlorodiethyl ether; alkanes which are liquid at ambient temperature, such as decane, heptane, dodecane, isododecane and cyclohexane; aromatic cyclic compounds which are liquid at ambient temperature, such as toluene and xylene; and aldehydes which are liquid at ambient temperature, such as benzaldehyde and acetaldehyde, and mixtures thereof.
- Besides the block polymer described above, the composition may comprise an additional polymer such as a film-forming polymer. According to the present invention a “film-forming polymer” is a polymer capable of forming, by itself or in the presence of an auxiliary film-forming agent, a continuous and adherent film on a support, particularly on keratin materials.
- Among the film-forming polymers which can be used in the composition of the present invention, mention may be made of synthetic polymers, of free-radical type or polycondensate type, and of polymers of natural origin, and mixtures thereof. As film-forming polymer, mention may be made in particular of acrylic polymers, polyurethanes, polyesters, polyamides, polyureas and cellulosic polymers such as nitro-cellulose.
- The polymer may be combined with one or more auxiliary film-forming agents. A film-forming agent of this kind may be selected from all of the compounds known to the person skilled in the art as being capable of fulfilling the desired function, and in particular may be selected from plasticizers and coalescers.
- The composition according to the invention may include at least one wax. By wax in the sense of the present invention is meant a lipophilic compound which is solid at ambient temperature (25° C.), exhibits a reversible solid/liquid state change and has a melting point greater than or equal to 30° C. and possibly up to 120° C.
- The melting point of the wax can be measured by means of a differential scanning calorimeter (DSC), an example being the calorimeter sold under the name DSC 30 by the company Mettler.
- The waxes may be hydrocarbon waxes, fluoro waxes and/or silicone waxes and may be vegetable, mineral, animal and/or synthetic in origin. In particular the waxes have a melting point of more than 25° C. and better still more than 45° C.
- As wax which can be used in the composition of the invention mention may be made of beeswax, carnauba wax or candelilla wax, paraffin, microcrystalline waxes, ceresin or ozokerite; synthetic waxes such as polyethylene waxes or Fischer-Tropsch waxes, and silicone waxes such as the alkyl- or alkoxydimethicones having 16 to 45 carbon atoms.
- The nature and amount of the solid fatty substances are a function of the desired mechanical properties and textures. By way of indication the composition may contain from 0% to 50% by weight of waxes, relative to the total weight of the composition, and better still from 1% to 30% by weight.
- The composition according to the invention may further comprise one or more colorants selected from water-soluble dyes and pulverulent colorants such as pigments, nacres and flakes, which are well known to the person skilled in the art. The colorants may be present in the composition in an amount ranging from 0.01% to 50% by weight, relative to the weight of the composition, preferably from 0.01% to 30% by weight.
- By pigments are meant particles of any form, white or coloured, organic or inorganic, which are insoluble in the physiological medium and are intended for colouring the composition.
- By nacres are meant iridescent particles of any form that are produced in particular by certain molluscs in their shell, or else are synthesized.
- The pigments may be white or coloured, organic and/or inorganic. Among inorganic pigments mention may be made of titanium dioxide, optionally in surface-treated form, zirconium oxide or cerium oxide, and also zinc oxide, iron oxides (black, yellow or red) or chromium oxide, manganese violet, ultramarine blue, chromium hydrate and ferric blue, and metal powders such as aluminium powder and copper powder.
- Among organic pigments mention may be made of carbon black, D & C pigments, and the cochineal carmine-based lakes of barium, strontium, calcium and aluminium.
- Mention may also be made of effect pigments, such as particles comprising an organic or inorganic, natural or synthetic substrate, for example glass, acrylic resins, polyester, polyurethane, polyethylene terephthalate, ceramics or aluminas, the said substrate being uncovered or covered with metallic substances such as aluminium, gold, silver, platinum, copper or bronze, or with metal oxides such as titanium dioxide, iron oxide or chromium oxide, and mixtures thereof.
- The nacreous pigments may be selected from white nacreous pigments such as titanium-covered mica, or bismuth oxychloride, coloured nacreous pigments such as titanium mica covered with iron oxides, titanium mica covered with, in particular, ferric blue or chromium oxide, titanium mica covered with an organic pigment of the aforementioned type, and also nacreous pigments based on bismuth oxychloride. It is also possible to use interference pigments, especially those which are liquid-crystal pigments or multi-layer pigments.
- The water-soluble dyes are, for example, beetroot juice and methylene blue.
- The composition according to the invention may further comprise one or more fillers, particularly in an amount ranging from 0.01% to 50% by weight, relative to the total weight of the composition, preferably ranging from 0.01% to 30% by weight. By fillers are meant particles of any form, colourless or white, mineral or synthetic, which are insoluble in the medium of the composition irrespective of the temperature at which the composition is manufactured. These fillers serve in particular to modify the rheology or texture of the composition.
- The fillers may be organic or inorganic and may be in any form, platelet-shaped, spherical or oblong, irrespective of the crystallographic form (for example leaf, cubic, hexagonal, orthorhombic, etc.). Mention may be made of talc, mica, silica, kaolin, polyamide (Nylon®) powders (Orgasol® from Atochem), poly-β-alanine and polyethylene, the powders of polymers of tetrafluoroethylene (Teflon®), lauroyl-lysine, starch, boron nitride, hollow polymeric microspheres such as those of polyvinylidene chloride/acrylonitrile, for instance Expancel® (Nobel Industrie), acrylic acid copolymers (Polytrap® from the company Dow Corning) and silicone resin microbeads (Tospearls® from Toshiba, for example), elastomeric polyorganosiloxane particles, precipitated calcium carbonate, magnesium carbonate and magnesium hydrocarbonate, hydroxyapatite, hollow silica microspheres (Silica Beads® from Maprecos), ceramic or glass microcapsules, metal soaps derived from organic carboxylic acids having 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, for example zinc stearate, magnesium stearate or lithium stearate, zinc laurate and magnesium myristate.
- The composition according to the invention may be in the form in particular of a stick, suspension, dispersion, solution, gel, emulsion, especially oil-in-water (O/W) or water-in-oil (W/O), or multiple (O/W/O or polyol/O/W or W/O/W), emulsion, or in the form of a cream, paste or mousse, or a vesicle dispersion, particularly of ionic or nonionic lipids, or a two-phase or multi-phase lotion, a spray, powder or paste, especially a flexible paste (in particular a paste having a dynamic viscosity at 25° C. of the order of 0.1 to 40 Pa·s at a shear rate of 200 s−1, after 10 minutes of measurement in cone/plate geometry). The composition may be anhydrous: for example, it may be an anhydrous paste.
- The person skilled in the art will be able to select the appropriate type of formulation, and the method of preparing it, on the basis of his or her general knowledge, taking into account, on the one hand, the nature of the constituents used, and especially their solubility in the vehicle, and, on the other hand, the application envisaged for the composition.
- The composition according to the invention may be a makeup composition such as products for the complexion (foundations), rouges, eyeshadows, lipsticks, concealers, blushers, mascaras, eyeliners, eyebrow makeup products, lip pencils, eye pencils, nail products, such as nail varnishes, body makeup products or hair makeup products (hair lacquer or mascara).
- The composition according to the invention may also be a facial or bodily skincare product, in particular a sun product or skin colouring product (such as a self-tanning product).
- The present invention likewise provides a cosmetic kit comprising:
- a container delimiting at least one compartment, the said container being closed by a closing element; and
- a composition as described above disposed inside the said compartment.
- The container may be in any appropriate form. It may in particular be in the form of a bottle, tube, jar, case, box, sachet or carton.
- The closing element may be in the form of a removable stopper, a lid, a cap, a tear-off strip or a capsule, particularly of the type comprising a body attached to the container and a cover cap articulated on the body. It may also be in the form of an element for selectively closing the container, particularly a pump, valve or valve flap.
- The container may be combined with an applicator, particularly in the form of a brush comprising an arrangement of bristles held by a twisted wire. A twisted brush of this kind is described in particular in patent U.S. Pat. No. 4,887,622. It may also be in the form of a comb comprising a plurality of application elements, obtained in particular from moulding. Combs of this kind are described, for example, in patent FR 2 796 529. The applicator may be in the form of a fine brush, as described, for example, in patent FR 2 722 380. The applicator may be in the form of a block of foam or elastomer, a felt or a spatula. The applicator may be free (tuft or sponge) or of one piece with a rod carried by the closing element, as described, for example, in patent U.S. Pat. No. 5,492,426. The applicator may be of one piece with the container, as described, for example, by patent FR 2 761 959.
- The product may be accommodated directly in the container, or indirectly. By way of example, the product may be arranged on an impregnated support, particularly in the form of a wipe or pad, and arranged (in unitary or plural form) in a box or in a sachet. A support of this kind, incorporating the product, is described for example in patent application WO 01/03538.
- The closing element may be coupled to the container by screwing. Alternatively the coupling between the closing element and the container is performed other than by screwing, in particular via a bayonet mechanism, by snap-fastening, gripping, welding, adhesive bonding, or by magnetic attraction. By “snap-fastening” is meant, in particular, any system involving the traversal of a bead or cord of material by elastic deformation of a portion, particularly of the closing element, followed by return to the elastically unstressed position of the said portion after the traversal of the bead or cord.
- The container may be at least partly made of thermoplastic material. Examples that may be mentioned of thermoplastic materials include polypropylene and polyethylene.
- Alternatively the container is made of a non-thermoplastic material, particularly of glass or of metal (or alloy).
- The container may be one with rigid walls or may have deformable walls, particularly in the form of a tube or tubular bottle.
- The container may include means intended for distributing, or facilitating the distribution of, the composition. By way of example, the container may have walls which are deformable so as to allow the composition to exit in response to a positive pressure inside the container, this positive pressure being brought about by elastic (or non-elastic) squeezing of the container's walls. Alternatively, and particularly when the product is in the form of a stick, the product may be driven by a piston mechanism. Still in the case of a stick, particularly a makeup product stick (lipstick, foundation, etc.), the container may include a mechanism, especially a rack mechanism, or one with a threaded rod, or with a helical groove, which is capable of displacing a stick in the direction of the said opening. A mechanism of this kind is described for example in patent FR 2 806 273 or in patent FR 2 775 566. A mechanism of this kind for a liquid product is described in patent FR 2 727 609.
- The container may be composed of a carton with a base delimiting at least one housing accommodating the composition, and a lid, particularly a lid articulated on the base, which is capable of covering the said base, at least in part. A carton of this kind is described for example in patent application WO 03/018423 or in patent FR 2 791 042.
- The container may be equipped with a drainer arranged in the region of the opening of the container. A drainer of this kind allows the applicator to be wiped and optionally allows the rod, which may be of one piece with it, to be wiped. A drainer of this kind is described for example in patent FR 2 792 618.
- The composition may be at the atmospheric pressure inside the container (at ambient temperature) or may be in pressurized form, particularly by means of a propellent gas (aerosol). In the latter case the container is equipped with a valve (of the type used for aerosols).
- The content of the patents or patent applications cited above is incorporated by reference into the present application.
- The examples which follow illustrate, without limitation, the compositions according to the invention.
-
INGREDIENTS % BY MASS Polymer from Example 4 50.0 Silica (Aerosil R 972 ®, Degussa) 5.0 Isododecane gelled with an ethylene/ 7.0 propylene/styrene copolymer and a butylene/ethylene/styrene copolymer (Versagel ® MD 970, Penreco) Hydrogenated polyisobutene 2.1 Octyldodecanol 0.9 Phenyltrimethicone (DC 556, 20 cSt, Dow 2.1 Corning) Isododecane 28.3 Vinylpyrrolidone/1-eicosene copolymer 1.2 (Antaron V-220 ®, ISP) Pigments 3.0 Perfume qs - The formula exhibits a much greater viscosity than the reference without gelling agent. It can also be applied without difficulty using a foam applicator, and leads to a homogeneous deposit.
-
Ingredients (% by weight) Glycerol 6 Propylene glycol 6 Acrylates/C10-C30 alkyl acrylate copolymer 0.3 PEMULEN TR-2 (Noveon) Ammonium polyacryloyldimethyltaurate polymer 0.3 (HOSTACERIN AMPS - Clariant) Cyclohexasiloxane (DOW CORNING 246 FLUID - Dow 6 Corning) Xanthan gum RHODICARE XC (Rhodia) 0.1 Terephthalylidene dicamphor sulphonic acid 1.5 (MEXORYL SX - Chimex) Triethanolamine qs Octocrylene (UVINUL N539 - BASF) 10 Butylmethoxydibenzoylmethane (Parsol 1789 - 2.5 Roche Vitamines) Drometrizole trisiloxane (MEXORYL XL - Chimex) 1.5 C12-C15 alkyl benzoate (FINSOLV TN - Witco) 4 Polymer from Example 3 1 Triethanolamine 0.35 Preservative and sequestrant qs Water qs 100 -
Polymer from Example 1 23.8 g of AS Butyl acetate 24.99 g Isopropanol 10.71 g Hexylene glycol 2.5 g DC RED 7 Lake 1 g Hectorite modified with stearyldimethyl- 1.3 g benzylammonium chloride (Bentone ® 27V from Elementis) -
Beeswax 8 g Paraffin wax 3 g Carnauba wax 6 g Hectorite modified with distearyldi- 5.3 g methylbenzylammonium chloride (Bentone ® 38V from Elementis) Propylene carbonate 1.7 g Filler 1 g Pigments 5 g Polymer from Example 2 12 g of AS Isododecane qs 100 -
Beeswax 8 g Paraffin wax 3 g Carnauba wax 6 g Hectorite modified with distearyldi- 5.3 g methylbenzylammonium chloride (Bentone ® 38V from Elementis) Propylene carbonate 1.7 g Filler 1 g Pigments 5 g Polymer from Example 4 12 g of AS Isododecane qs 100 -
Polymer from Example 5 23.8 g of AS Butyl acetate 24.99 g Isopropanol 10.71 g Hexylene glycol 2.5 g DC RED 7 Lake 1 g Hectorite modified with stearyldimethyl- 1.3 g benzylammonium chloride (Bentone ® 27V from Elementis) Ethyl acetate qs 100 g -
Beeswax 8 g Paraffin wax 3 g Carnauba wax 6 g Hectorite modified with distearyldi- 5.3 g methylbenzylammonium chloride (Bentone ® 38V from Elementis) Propylene carbonate 1.7 g Filler 1 g Pigments 5 g Polymer from Example 6 12 g of AS Isododecane qs 100
Claims (101)
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US10/529,218 Abandoned US20060115444A1 (en) | 2002-09-26 | 2003-09-26 | Glossy liquid composition comprising a sequenced polymer |
US10/528,699 Abandoned US20060134032A1 (en) | 2002-09-26 | 2003-09-26 | Nail varnish composition comprising a sequenced polymer |
US10/529,267 Abandoned US20060099164A1 (en) | 2002-09-26 | 2003-09-26 | Composition for coating keratin fibres, comprising a high dry extract that contains a sequenched polymer |
US10/529,318 Expired - Fee Related US7875265B2 (en) | 2002-09-26 | 2003-09-26 | Cosmetic composition comprising a sequenced polymer and a plasticizer |
US10/529,264 Abandoned US20060147403A1 (en) | 2002-09-26 | 2003-09-26 | Non-transfer cosmetic composition comprising a sequenced polymer |
US10/670,388 Abandoned US20040120906A1 (en) | 2002-09-26 | 2003-09-26 | Nail varnish composition comprising a block polymer |
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US10/529,267 Abandoned US20060099164A1 (en) | 2002-09-26 | 2003-09-26 | Composition for coating keratin fibres, comprising a high dry extract that contains a sequenched polymer |
US10/529,318 Expired - Fee Related US7875265B2 (en) | 2002-09-26 | 2003-09-26 | Cosmetic composition comprising a sequenced polymer and a plasticizer |
US10/529,264 Abandoned US20060147403A1 (en) | 2002-09-26 | 2003-09-26 | Non-transfer cosmetic composition comprising a sequenced polymer |
US10/670,388 Abandoned US20040120906A1 (en) | 2002-09-26 | 2003-09-26 | Nail varnish composition comprising a block polymer |
US10/528,698 Abandoned US20060127334A1 (en) | 2002-09-26 | 2003-09-26 | Lipstick comprising a sequenced polymer |
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AU (10) | AU2003290143A1 (en) |
BR (2) | BR0303890A (en) |
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WO (10) | WO2004028492A2 (en) |
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WO2024049867A1 (en) | 2022-08-31 | 2024-03-07 | L'oreal | Cosmetic compositions with improved wear and transfer resistance |
FR3142901A1 (en) | 2022-12-09 | 2024-06-14 | L'oreal | COSMETIC COMPOSITIONS WITH BETTER RESISTANCE TO WEAR AND TRANSFER |
Citations (87)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2047398A (en) * | 1930-06-26 | 1936-07-14 | Ig Farbenindustrie Ag | Artificial resins and process of making them |
US2528378A (en) * | 1947-09-20 | 1950-10-31 | John J Mccabe Jr | Metal salts of substituted quaternary hydroxy cycloimidinic acid metal alcoholates and process for preparation of same |
US2723248A (en) * | 1954-10-01 | 1955-11-08 | Gen Aniline & Film Corp | Film-forming compositions |
US2781354A (en) * | 1956-03-26 | 1957-02-12 | John J Mccabe Jr | Imidazoline derivatives and process |
US3673160A (en) * | 1970-02-12 | 1972-06-27 | Rhodiaceta | Process for producing brilliant sulfonated polyamide-imide fibers and such fibers so produced |
US3716633A (en) * | 1966-08-03 | 1973-02-13 | I Oreal Sa | Vinyl acetate-crotonic acid-unsaturated ester or ether polymers in hair lacquers and setting lotions |
US3802841A (en) * | 1971-06-14 | 1974-04-09 | Rhone Poulenc Textile | Nitro aromatic hydrocarbon,amino nitro aromatic & nitro aromatic phosphine oxides on aromatic polyamide-imide as light fading inhibitors for dyes thereon |
US3836537A (en) * | 1970-10-07 | 1974-09-17 | Minnesota Mining & Mfg | Zwitterionic polymer hairsetting compositions and method of using same |
US3910862A (en) * | 1970-01-30 | 1975-10-07 | Gaf Corp | Copolymers of vinyl pyrrolidone containing quarternary ammonium groups |
US3915921A (en) * | 1974-07-02 | 1975-10-28 | Goodrich Co B F | Unsaturated carboxylic acid-long chain alkyl ester copolymers and tri-polymers water thickening agents and emulsifiers |
US3937811A (en) * | 1973-06-08 | 1976-02-10 | Societe Anonyme Dite: L'oreal | Fatty compositions for use in cosmetic makeup compositions and said cosmetic makeup compositions |
US3946749A (en) * | 1972-06-20 | 1976-03-30 | L'oreal | Hair cosmetic compositions based on grafted and crosslinked copolymers |
US3966404A (en) * | 1974-04-01 | 1976-06-29 | L'oreal | Hair laquer or hair setting composition containing a terpolymer |
US3966403A (en) * | 1974-04-01 | 1976-06-29 | L'oreal | Hair lacquer or hair setting composition containing a tetrapolymer |
US4031307A (en) * | 1976-05-03 | 1977-06-21 | Celanese Corporation | Cationic polygalactomannan compositions |
US4030512A (en) * | 1974-12-30 | 1977-06-21 | Societe Anonyme Dite: L'oreal | Hair lacquer or setting lotion containing bi- or tri-sequenced copolymer |
US4032628A (en) * | 1970-04-07 | 1977-06-28 | Societe Anonyme Dite: L'oreal | Cosmetic emulsion compositions including black polymer emulsifiers |
US4070533A (en) * | 1974-04-01 | 1978-01-24 | L'oreal | Terpolymer of (a) crotonic acid (b) vinyl acetate and (c) allyl or methallyl esters |
US4076912A (en) * | 1974-04-01 | 1978-02-28 | L'oreal | Tetrapolymers comprising (a) unsaturated acids (b) vinyl esters (c) branched allyl or methallyl esters and (d) vinyl ether or vinyl fatty ester or linear allyl or methallyl esters |
US4137208A (en) * | 1976-05-06 | 1979-01-30 | Berger, Jenson & Nicholson Limited | Coating composition |
US4282203A (en) * | 1978-10-27 | 1981-08-04 | L'oreal | Hair lacquer and hair lotion compositions containing a copolymer having units of a vinyl allyl or methally ester of an α- or β-cyclic carboxylic acid |
US4289752A (en) * | 1976-04-06 | 1981-09-15 | Societe Anonyme Dite: L'oreal | Cosmetic compositions containing N-alkylacrylamide or N-alkylmethacrylamide based copolymers |
US4296053A (en) * | 1979-05-24 | 1981-10-20 | Brown Group, Inc. | Method of making foamed plastisol insoles for shoes |
US4459249A (en) * | 1982-01-22 | 1984-07-10 | Inoue Mtp Kabushiki Kaisha | Method of manufacturing a foamed protective and decorative molding for an automobile |
US4524037A (en) * | 1982-08-16 | 1985-06-18 | Michel Marc | Method and apparatus for forming a flexible thermoplastic resin foam article using an RF field |
US4525231A (en) * | 1983-06-08 | 1985-06-25 | Voplex Corporation | Method of making cushioned automotive strap handle |
US4824617A (en) * | 1986-07-30 | 1989-04-25 | Inoue Mtp Kabushiki Kaisha | Method for manufacturing plastic foam |
US5110582A (en) * | 1981-03-25 | 1992-05-05 | Basf Aktiengesellschaft | Hair-setting preparation |
US5266321A (en) * | 1988-03-31 | 1993-11-30 | Kobayashi Kose Co., Ltd. | Oily make-up cosmetic comprising oil base and silicone gel composition |
US5468477A (en) * | 1992-05-12 | 1995-11-21 | Minnesota Mining And Manufacturing Company | Vinyl-silicone polymers in cosmetics and personal care products |
US5492426A (en) * | 1993-02-22 | 1996-02-20 | L'oreal | Deformable applicator with capillary feed |
US5519063A (en) * | 1991-07-25 | 1996-05-21 | L'oreal | Oily cosmetic composition containing, as a thickener, an association of two copolymers and optionally containing an amphiphilic rheology corrector |
US5538717A (en) * | 1993-10-15 | 1996-07-23 | L'oreal | Aqueous nail polish containing as film-forming substance particles of polyester-polyurethane which are anionic in dispersion |
US5681877A (en) * | 1993-09-30 | 1997-10-28 | Lvmh Recherche | Use of acrylic block copolymers as wetting and/or dispersing agents for solid particles, and resulting dispersions |
US5772347A (en) * | 1994-12-06 | 1998-06-30 | L'oreal | Dispenser for a product with a liquid-to-pasty consistency |
US5783657A (en) * | 1996-10-18 | 1998-07-21 | Union Camp Corporation | Ester-terminated polyamides of polymerized fatty acids useful in formulating transparent gels in low polarity liquids |
US5843407A (en) * | 1993-10-18 | 1998-12-01 | The Procter & Gamble Company | Non-sweating lipsticks |
US5879095A (en) * | 1994-12-06 | 1999-03-09 | L'oreal | Dispenser for a product of liquid-to-pasty consistency, equipped with an application tip |
US6027739A (en) * | 1995-05-15 | 2000-02-22 | Lip Ink International | Smear-resistant cosmetic |
US6059473A (en) * | 1994-07-12 | 2000-05-09 | L'oreal | Applicator for applying a liquid cosmetic product and make-up assembly provided with such an applicator |
US6074654A (en) * | 1995-11-07 | 2000-06-13 | The Procter & Gamble Company | Transfer resistant cosmetic compositions |
US6083516A (en) * | 1997-03-26 | 2000-07-04 | Avon Products, Inc. | Wear resistant cosmetics |
US6106813A (en) * | 1993-08-04 | 2000-08-22 | L'oreal | Polyester polyurethanes, process for preparing them, produced from the said polyester polyurethanes and their use in cosmetic compositions |
US6106820A (en) * | 1997-05-12 | 2000-08-22 | Procter & Gamble Company | Cosmetic compositions |
US6139849A (en) * | 1996-02-22 | 2000-10-31 | L'oreal | Cosmetic composition for fixing and sheen |
US6153206A (en) * | 1997-08-27 | 2000-11-28 | Revlon Consumer Products Corporation | Cosmetic compositions |
US6174968B1 (en) * | 1999-08-24 | 2001-01-16 | Shell Oil Company | Oil gel formulations containing polysiloxane block copolymers dissolved in hydrogenated silicone oils |
US6225390B1 (en) * | 1998-05-08 | 2001-05-01 | Shell Oil Company | Oil gel formulations containing polystyrene-polydimethylsiloxane or polyethylene-polydimethylsiloxane block copolymers dissolved in siloxane monomers |
US6228967B1 (en) * | 1996-05-22 | 2001-05-08 | Mona Industries, Inc. | Organosilicone having a carboxyl functional group thereon |
US6238679B1 (en) * | 1998-03-09 | 2001-05-29 | L'oreal S.A. | Film-forming composition comprising a polyurethane in aqueous dispersion and a plasticizer |
US6267951B1 (en) * | 1997-03-26 | 2001-07-31 | Avon Products, Inc. | Cosmetic composition for the nails and hair |
US6268466B1 (en) * | 1999-01-04 | 2001-07-31 | Arizona Chemical Company | Tertiary amide terminated polyamides and uses thereof |
US6299807B1 (en) * | 1996-11-01 | 2001-10-09 | Honda Giken Kogyo Kabushiki Kaisha | Method for producing molded article |
US6303105B1 (en) * | 1997-03-26 | 2001-10-16 | Avon Products, Inc. | Cosmetic composition for imparting wear resistance and shine |
US6319959B1 (en) * | 1995-06-27 | 2001-11-20 | L'oréal | Cosmetic or dermatological compositions of polyurethane and/or polyurea block polycondensation products containing silicon grafts and their use |
US20020015611A1 (en) * | 2000-03-16 | 2002-02-07 | Gilles Blondeel | Device for packaging and applying a cosmetic or care product |
US20020018759A1 (en) * | 2000-05-04 | 2002-02-14 | Pagano Frank Charles | Nail enamel compositions, related methods, and a two component kit for painting the nails |
US6372876B1 (en) * | 1992-07-29 | 2002-04-16 | Basf Aktiengesellschaft | Use of polyurethanes which are soluble or dispersible in water as aids in cosmetic and pharmaceutical compositions, and polyurethanes which contain polylactic acid polyols as copolymerized units |
US20020055562A1 (en) * | 1998-10-29 | 2002-05-09 | Butuc S. Gina | Gel compositions |
US6386781B1 (en) * | 1997-04-15 | 2002-05-14 | L'oreal | Unit for packaging and applying a liquid product |
US20020061319A1 (en) * | 2000-09-29 | 2002-05-23 | Pascale Bernard | Film-forming cosmetic composition |
US6395265B1 (en) * | 1996-01-05 | 2002-05-28 | L'oreal | Cosmetic compositions containing multi-block ionizable polysiloxane/polyurethane and/or polyurea polycondensates in solution, and uses thereof |
US20020076425A1 (en) * | 2000-09-28 | 2002-06-20 | Jean Mondet | Cosmetic compositions comprising at least one continuous liquid fatty phase structured with polyurethanes, polyurethaneureas, and polyureas |
US20020115780A1 (en) * | 2000-05-23 | 2002-08-22 | Nathalie Mougin | Use in cosmetics of block ethylene copolemers with elastic character and compositions containing same |
US6484731B1 (en) * | 1999-03-16 | 2002-11-26 | L'oreal | Single-piece articulated assembly |
US20030017182A1 (en) * | 2000-11-10 | 2003-01-23 | Florence Tournilhac | Cosmetic composition structured by a thermotropic liquid crystal polymer |
US20030017124A1 (en) * | 2001-04-10 | 2003-01-23 | L'oreal | Two-coat make-up product containing a goniochromatic pigment and monochrome pigment, and make-up kit containing this product |
US20030059392A1 (en) * | 2001-07-18 | 2003-03-27 | L'oreal | Composition for topical use containing a diblock polymer |
US6552146B1 (en) * | 1999-04-06 | 2003-04-22 | L'oreal S.A. | Composition comprising polymers having a star structure, the polymers, and their use |
US20030113285A1 (en) * | 2000-05-08 | 2003-06-19 | Helmut Meffert | Polyurethane and the use thereof for modifying rheological properties |
US6581610B1 (en) * | 1999-07-21 | 2003-06-24 | L'oreal S.A. | Applicator, applicator system, and method for applying a product to the eyelashes |
US20030124079A1 (en) * | 2000-07-21 | 2003-07-03 | Nathalie Mougin | Novel cationic associative polyurethanes and their use as thickeners |
US20030124074A1 (en) * | 2001-11-29 | 2003-07-03 | L'oreal | Adhesive block ethylenic copolymers, cosmetic compositions containing them and cosmetic use of these copolymers |
US20040009136A1 (en) * | 2002-05-31 | 2004-01-15 | L'oreal | Aqueous hair treatment compositions, thickened with an amphiphilic linear block copolymer |
US20040014872A1 (en) * | 2000-06-16 | 2004-01-22 | Raether Roman Benedikt | Bonding agent composition containing solid matter, with radically polymerised block copolymers |
US6685925B2 (en) * | 2000-10-03 | 2004-02-03 | Jean M. J. Frechet | Cosmetic and personal care compositions |
US6692733B1 (en) * | 1999-04-06 | 2004-02-17 | L'oreal | Composition comprising polymers having a star structure, the polymers, and their use |
US20040039101A1 (en) * | 2002-05-31 | 2004-02-26 | Claude Dubief | Washing compositions comprising at least one amphiphilic block copolymer and at least one cationic or amphoteric polymer |
US20040052752A1 (en) * | 2000-07-18 | 2004-03-18 | Henri Samain | Cosmetic composition containing a block copolymer consisting of blocks with different refractive indices |
US20040077788A1 (en) * | 2002-07-19 | 2004-04-22 | Cid Centro De Investigacion Y Desarrollo Tecnologico, S.A. De. C.V. | Block copolymers containing functional groups |
US20040093676A1 (en) * | 2001-04-03 | 2004-05-20 | Laurent Vidal | Novel dyeing composition for dyeing keratinous fibres comprising a particular dicationic monoazo dye |
US20040120920A1 (en) * | 2002-09-26 | 2004-06-24 | Bertrand Lion | Novel block polymers and cosmetic compositions and processes comprising them |
US20050020779A1 (en) * | 2001-11-29 | 2005-01-27 | Nathalie Mougin | Block ethylenic copolymers cosmetic compositions containing them and cosmetic use of these copolymers |
US20050106197A1 (en) * | 2003-09-26 | 2005-05-19 | Xavier Blin | Cosmetic composition comprising a block polymer and a non-volatile silicone oil |
US20050220747A1 (en) * | 2004-03-25 | 2005-10-06 | Bertrand Lion | Styling composition comprising, in a predominantly aqueous medium, a pseudo-block polymer, processes employing same and uses thereof |
US6960339B1 (en) * | 1999-07-15 | 2005-11-01 | L'oreal S.A. | Compositions structured with at least one polymer and methods of using the same |
US20060093568A1 (en) * | 2002-09-26 | 2006-05-04 | Xavier Blin | Composition comprising a block polymer and a film-forming agent |
Family Cites Families (197)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US811910A (en) * | 1903-03-12 | 1906-02-06 | Albert H Emery | Cartridge. |
FR1222944A (en) | 1958-04-15 | 1960-06-14 | Hoechst Ag | Graft polymers and their preparation process |
FR1400366A (en) | 1963-05-15 | 1965-05-28 | Oreal | New compounds which can be used in particular for the treatment of hair |
US4129711A (en) | 1965-03-03 | 1978-12-12 | L'oreal | Polymers comprising vinyl esters-crotonic acid |
LU54202A1 (en) | 1967-07-28 | 1969-03-24 | Oreal | Process for the preparation of new copolymers and cosmetic compositions containing these copolymers |
US3925542A (en) | 1965-03-03 | 1975-12-09 | Oreal | Hair lacquer and wave setting compositions containing vinyl acetate-crotonic acid-containing polymers |
NL136457C (en) | 1967-03-23 | |||
SE375780B (en) | 1970-01-30 | 1975-04-28 | Gaf Corp | |
FR2079785A5 (en) | 1970-02-12 | 1971-11-12 | Rhodiaceta | Lustrous polyamide-imide based fibres by new process |
LU60676A1 (en) | 1970-04-07 | 1972-02-10 | ||
FR2140977A5 (en) | 1971-10-26 | 1973-01-19 | Oreal | Sequenced polymers - from lipophilic and hydrophilic monomers for cosmetic use |
CA981183A (en) | 1972-04-14 | 1976-01-06 | Albert L. Micchelli | Hair fixing compositions |
USRE29871E (en) | 1973-06-08 | 1978-12-26 | L'oreal | Fatty compositions for use in cosmetic makeup compositions and said cosmetic makeup compositions |
AT364706B (en) | 1976-04-06 | 1981-11-10 | Oreal | COSMETIC AGENT FOR TREATING THE HAIR |
LU75371A1 (en) | 1976-07-12 | 1978-02-08 | ||
LU75370A1 (en) | 1976-07-12 | 1978-02-08 | ||
FR2357241A2 (en) | 1976-07-08 | 1978-02-03 | Oreal | Partially esterified or amidated unsaturated anhydride copolymer - for hair lacquer made from copolymer of unsaturated anhydride, allyl or methallyl ester and acrylamide or methacrylamide cpd. |
US4152416A (en) * | 1976-09-17 | 1979-05-01 | Marra Dorothea C | Aerosol antiperspirant compositions delivering astringent salt with low mistiness and dustiness |
US4128631A (en) | 1977-02-16 | 1978-12-05 | General Mills Chemicals, Inc. | Method of imparting lubricity to keratinous substrates and mucous membranes |
CA1091160A (en) | 1977-06-10 | 1980-12-09 | Paritosh M. Chakrabarti | Hair preparation containing vinyl pyrrolidone copolymer |
US4165367A (en) | 1977-06-10 | 1979-08-21 | Gaf Corporation | Hair preparations containing vinyl pyrrolidone copolymer |
US4223009A (en) | 1977-06-10 | 1980-09-16 | Gaf Corporation | Hair preparation containing vinyl pyrrolidone copolymer |
US4131576A (en) | 1977-12-15 | 1978-12-26 | National Starch And Chemical Corporation | Process for the preparation of graft copolymers of a water soluble monomer and polysaccharide employing a two-phase reaction system |
FR2478998A1 (en) | 1980-04-01 | 1981-10-02 | Oreal | ANHYDROUS NAIL VARNISH |
EP0080976B1 (en) | 1981-11-30 | 1986-09-24 | Ciba-Geigy Ag | Mixtures of quaternary polymeric acrylic ammonium salts, quaternary mono- or oligomeric ammonium salts and surfactants, their preparation and their use in cosmetic compositions |
US4509949A (en) | 1983-06-13 | 1985-04-09 | The B. F. Goodrich Company | Water thickening agents consisting of copolymers of crosslinked acrylic acids and esters |
US4514552A (en) | 1984-08-23 | 1985-04-30 | Desoto, Inc. | Alkali soluble latex thickeners |
US4592426A (en) * | 1984-12-10 | 1986-06-03 | Hughes Tool Company | Upper termination with sliding sleeve seals |
US4728571A (en) | 1985-07-19 | 1988-03-01 | Minnesota Mining And Manufacturing Company | Polysiloxane-grafted copolymer release coating sheets and adhesive tapes |
AU612965B2 (en) | 1985-08-12 | 1991-07-25 | Ciba Specialty Chemicals Water Treatments Limited | Polymeric thickeners and their production |
US4693935A (en) | 1986-05-19 | 1987-09-15 | Minnesota Mining And Manufacturing Company | Polysiloxane-grafted copolymer pressure sensitive adhesive composition and sheet materials coated therewith |
FR2607373B1 (en) | 1986-11-28 | 1989-02-24 | Oreal | BRUSH FOR APPLYING MASCARA ON EYELASHES |
JPS63313710A (en) | 1987-06-16 | 1988-12-21 | Toray Silicone Co Ltd | Face cleaning cosmetic |
LU87030A1 (en) * | 1987-10-28 | 1989-05-08 | Oreal | USE IN COSMETICS OF NEW SUBSTANCES AS INFRARED RADIATION REFLECTORS, COSMETIC COMPOSITIONS CONTAINING THEM AND THEIR USE FOR THE PROTECTION OF THE HUMAN SKIN AGAINST INFRARED RADIATION |
EP0320218A3 (en) | 1987-12-11 | 1990-04-25 | The Procter & Gamble Company | Low glass transition temperature adhesive copolymers for use in hair styling products |
US5061481A (en) | 1989-03-20 | 1991-10-29 | Kobayashi Kose Co., Ltd. | Cosmetic composition having acryl-silicone graft copolymer |
US5219560A (en) | 1989-03-20 | 1993-06-15 | Kobayashi Kose Co., Ltd. | Cosmetic composition |
US5156911A (en) | 1989-05-11 | 1992-10-20 | Landec Labs Inc. | Skin-activated temperature-sensitive adhesive assemblies |
US4981902A (en) * | 1989-08-07 | 1991-01-01 | Minnesota Mining And Manufacturing Company | Polysiloxane-grafted copolymer non-pressure sensitive topical binder composition and method of coating therewith |
DE69033073T2 (en) | 1989-08-07 | 1999-11-25 | Procter & Gamble | Hair care and fixative |
US5209924A (en) * | 1989-08-07 | 1993-05-11 | Minnesota Mining And Manufacturing Company | Polysiloxane-grafted copolymer topical binder composition with novel fluorochemical comonomer and method of coating therewith |
US4972037A (en) | 1989-08-07 | 1990-11-20 | Minnesota Mining And Manufacturing Company | Polysiloxane-grafted copolymer topical binder composition with novel fluorochemical comonomer and method of coating therewith |
US4981903A (en) * | 1989-08-07 | 1991-01-01 | Minnesota Mining And Manufacturing Company | Polysiloxane-grafter copolymer topical binder composition with novel hydrophilic monomers and method of coating therewith |
EP0412707B1 (en) | 1989-08-07 | 1994-02-09 | The Procter & Gamble Company | Hair conditioning and styling compositions |
FR2685354B1 (en) | 1991-12-24 | 1996-03-29 | Rhone Poulenc Fibres | PROCESS FOR SPINNING POLYAMIDE-IMIDE (PAI) SOLUTIONS BASED ON TOLUYLENE OR METAPHENYLENE DIISOCYANATES AND FIBERS THUS OBTAINED. |
US5756635A (en) * | 1991-12-24 | 1998-05-26 | Rhone-Poulenc Fibres | Process for spinning from solution of polyamide-imides (PAI) based on tolylene or met-phenylene diisocyanates and fibres thus obtained |
US6258916B1 (en) | 1991-12-24 | 2001-07-10 | Rhone-Poulenc Fibres | Process for spinning from solution of polyamide-imides (PAI) based on tolylene or meta-phenylene diisocyanates and fibers thus obtained |
JP3098604B2 (en) | 1992-02-13 | 2000-10-16 | 株式会社コーセー | Lipstick overcoat |
JPH07508027A (en) | 1992-05-12 | 1995-09-07 | ミネソタ マイニング アンド マニュファクチャリング カンパニー | Polymers in cosmetics and personal care products |
CZ277394A3 (en) | 1992-05-15 | 1995-08-16 | Procter & Gamble | Adhesives containing grafted polysiloxane polymer and cosmetic mixtures prepared therefrom |
DE4220807A1 (en) * | 1992-06-25 | 1994-01-05 | Basf Ag | Vinyl polymers produced in a two-stage procedure and their use as paint binders |
EP0582152B1 (en) | 1992-07-28 | 2003-04-16 | Mitsubishi Chemical Corporation | A hair cosmetic composition |
JP3393903B2 (en) | 1992-11-30 | 2003-04-07 | 株式会社資生堂 | Makeup cosmetics |
US6663885B1 (en) | 1993-03-15 | 2003-12-16 | A. Natterman & Cie Gmbh | Aqueous liposome system and a method for the preparation of such a liposome system |
JP3214674B2 (en) | 1993-03-26 | 2001-10-02 | 出光興産株式会社 | Novel styryl compound, method for producing the same and organic electroluminescent device comprising the same |
JPH06279232A (en) * | 1993-03-30 | 1994-10-04 | Nisshin Chem Ind Co Ltd | Eye makeup cosmetic |
EP0619111B2 (en) | 1993-04-06 | 2005-09-14 | National Starch and Chemical Investment Holding Corporation | Use of polyurethanes with carboxylate functionality for hair fixative applications |
US5374388A (en) * | 1993-04-22 | 1994-12-20 | Lockheed Corporation | Method of forming contoured repair patches |
US5476901A (en) | 1993-06-24 | 1995-12-19 | The Procter & Gamble Company | Siloxane modified polyolefin copolymers |
US5472798A (en) | 1993-07-16 | 1995-12-05 | Nissan Motor Co., Ltd. | Coloring structure having reflecting and interfering functions |
FR2708615B1 (en) | 1993-08-04 | 1995-09-15 | Oreal | New polyester-polyurethanes, their preparation process, pseudo-latex made from said polyester-polyurethanes and their use in cosmetic compositions. |
KR100295938B1 (en) | 1993-08-23 | 2001-10-24 | 데이비드 엠 모이어 | Silicone grafted thermoplastic elastomers and hair and skin protective compositions containing them |
FR2710646B1 (en) | 1993-10-01 | 1995-12-22 | Lvmh Rech | Stable microdispersions and microgels based on acrylic polymers, process for obtaining them and compositions, in particular cosmetic, containing them. |
JP3410189B2 (en) | 1993-12-28 | 2003-05-26 | 株式会社コーセー | Eye makeup cosmetics |
FR2715063B1 (en) * | 1994-01-17 | 1996-03-22 | Oreal | Cosmetic composition for make-up in the form of a mascara containing at least one wax and one pseudo-latex of cellulose derivatives. |
FR2715306B1 (en) | 1994-01-25 | 1996-03-15 | Oreal | Cosmetic or dermopharmaceutical composition in the form of a flexible paste and process for the preparation of said composition. |
US6160054A (en) | 1995-05-08 | 2000-12-12 | Fmc Corporation | Hetero-telechelic polymers and processes for making same |
JPH07309721A (en) | 1994-05-17 | 1995-11-28 | Kao Corp | Two-pack type nail-beautifying agent |
JP3166482B2 (en) | 1994-06-07 | 2001-05-14 | 日産自動車株式会社 | Coloring structure having reflective interference action |
FR2724843A1 (en) | 1994-09-28 | 1996-03-29 | Lvmh Rech | NAIL VARNISH CONTAINING MICROGELS |
JPH08119836A (en) | 1994-10-21 | 1996-05-14 | Nippon Oil & Fats Co Ltd | Cosmetic composition for nail |
FR2727609B1 (en) | 1994-12-06 | 1997-01-10 | Oreal | DISPENSING ASSEMBLY FOR THE APPLICATION OF A LIQUID CONSISTENT TO PASTE |
US5686067A (en) | 1995-01-05 | 1997-11-11 | Isp Investments Inc. | Low voc hair spray compositions |
FR2733683B1 (en) | 1995-05-05 | 1997-06-06 | Oreal | NAIL VARNISH COMPOSITION COMPRISING A CROSSLINKED POLYESTER |
CN1070520C (en) | 1995-06-15 | 2001-09-05 | 雷伊化学有限公司 | Gels made from triblock copolymers |
US5969068A (en) | 1995-06-19 | 1999-10-19 | The Lubrizol Corporation | Dispersant-viscosity improvers for lubricating oil compositions |
US5849275A (en) | 1995-06-26 | 1998-12-15 | Revlon Consumer Products Corporation | Glossy transfer resistant cosmetic compositions |
TW413692B (en) | 1995-06-30 | 2000-12-01 | Chiba Seifun Kk | Novel silicone derivatives, their production and use |
CZ140498A3 (en) | 1995-11-07 | 1998-10-14 | The Procter & Gamble Company | Stable cosmetic preparations |
US5690918A (en) | 1995-12-19 | 1997-11-25 | Maybelline, Inc. | Solvent-based non-drying lipstick |
JP3605938B2 (en) | 1996-03-29 | 2004-12-22 | 株式会社コーセー | Eyelash cosmetics |
US5849318A (en) | 1996-06-26 | 1998-12-15 | Kao Corporation | Oil-based solid cosmetic composition |
DE19638795A1 (en) | 1996-09-20 | 1998-03-26 | Basf Ag | Aqueous or aqueous / alcoholic hair cosmetic formulation |
BR9705926A (en) | 1996-11-26 | 1999-04-27 | Oreal | Topical composition use and process to limit decrease and / or prevent the transfer of a composition |
FR2756176B1 (en) | 1996-11-26 | 1998-12-18 | Oreal | COSMETIC COMPOSITION COMPRISING A FLUORINATED COMPOUND AND HAVING IMPROVED COMFORT |
FR2758083B1 (en) | 1997-01-03 | 1999-02-05 | Oreal | COSMETIC AND / OR DERMATOLOGICAL COMPOSITION CONTAINING A DISPERSION OF A POLYMERIC SYSTEM AND USE OF THE SYSTEM AS A TENSIONER |
US5736125A (en) | 1997-01-10 | 1998-04-07 | National Starch And Chemical Investment Holding Corporation | Compositions containing copolymers as a thickening agent |
CN1224343A (en) * | 1997-01-20 | 1999-07-28 | 莱雅公司 | Cosmetic composition contg. as coating agent for keratinous fibre a film-forming mixture consisting of polymer particles capable of being film-forming and particles not capable of being film-formed |
US6140431A (en) | 1997-02-27 | 2000-10-31 | Rohm And Haas Company | Process for preparing continuously variable-composition copolymers |
US6433068B1 (en) | 1997-03-07 | 2002-08-13 | David S. Morrison | Hydrocarbon gels as suspending and dispersing agents and products |
US5879670A (en) | 1997-03-31 | 1999-03-09 | Calgon Corporation | Ampholyte polymers for use in personal care products |
DE69839333T2 (en) | 1997-05-30 | 2009-07-09 | Shiseido Co. Ltd. | COMPOSITION OF A COPOLYMER CONTAINING THE REACTIVE SILYL GROUP AND METHODS OF USE |
JPH11124312A (en) | 1997-10-20 | 1999-05-11 | Shiseido Co Ltd | Pack cosmetic and its treatment |
JPH11100307A (en) * | 1997-09-29 | 1999-04-13 | Kao Corp | Film-forming agent and cosmetic |
FR2774587B1 (en) | 1998-02-09 | 2000-03-10 | Oreal | USE OF A WAX MICRODISPERSION IN A COSMETIC OR DERMATOLOGICAL COMPOSITION |
FR2774588B1 (en) | 1998-02-11 | 2000-05-05 | Oreal | COSMETIC OR DERMATOLOGICAL COMPOSITION CONTAINING AT LEAST ONE NATURAL, RECOMBINANT ARACHNID SILK PROTEIN OR THE LIKE |
FR2775566B1 (en) | 1998-03-03 | 2000-05-12 | Oreal | GRAPE HOLDER CUP AND PACKAGING ASSEMBLY FOR A MAKEUP PRODUCT COMPRISING SAME |
FR2776509B1 (en) | 1998-03-31 | 2001-08-10 | Oreal | TOPICAL COMPOSITION CONTAINING AN ESTER OF FATTY ACID OR ALCOHOL BRANCHED IN C24 TO C28 |
EP0951897B1 (en) | 1998-04-21 | 2003-09-03 | L'oreal | Topical composition containing an olefinic copolymer with controlled crystallisation |
CA2276568C (en) | 1998-07-03 | 2007-01-02 | Kuraray Co., Ltd. | Block copolymer and polymer composition comprising the same |
FR2782003B1 (en) * | 1998-08-10 | 2000-10-13 | Oreal | NON-TRANSFER MAKEUP OR CARE COMPOSITION BASED ON ISOPARAFFINS AND FUNCTIONALIZED SYNTHETIC WAXES |
US6068421A (en) | 1998-08-25 | 2000-05-30 | Rexam Cosmetic Packaging, Inc. | Protective shell for a cosmetic container |
WO2000026285A1 (en) * | 1998-10-29 | 2000-05-11 | Penreco | Gel compositions |
AU1316199A (en) * | 1998-11-12 | 2000-06-05 | Procter & Gamble Company, The | Cosmetic compositions |
DE19903391A1 (en) | 1999-01-29 | 2000-08-03 | Bayer Ag | Aqueous coating agent, process for its preparation and its use |
US6423306B2 (en) * | 1999-02-26 | 2002-07-23 | L'oreal Sa | Cosmetic compositions containing di-block, tri-block, multi-block and radial block copolymers |
JP2002539299A (en) | 1999-03-18 | 2002-11-19 | カリフォルニア インスティチュート オブ テクノロジー | ABA-type triblock and diblock copolymers and method for producing the same |
FR2792190B1 (en) | 1999-04-16 | 2001-09-28 | Sophim | PROCESS FOR THE MANUFACTURE OF A NON-FATTY EMOLLIENT BASED ON WAX-ESTERS |
FR2792618B1 (en) | 1999-04-23 | 2001-06-08 | Oreal | DEVICE FOR PACKAGING AND APPLYING A PRODUCT HAVING A SPIN-OUT MEMBER COMPRISING A SLOT |
US6197883B1 (en) | 1999-06-03 | 2001-03-06 | Ppg Industries Ohio, Inc. | Thermosetting coating compositions containing flow modifiers prepared by controlled radical polymerization |
US6254878B1 (en) * | 1999-07-01 | 2001-07-03 | E. I. Du Pont De Nemours And Company | Nail polish compositions containing acrylic polymers |
FR2795957B1 (en) | 1999-07-08 | 2001-09-28 | Oreal | MAKEUP COMPOSITION COMPRISING FIBERS |
EP1199956A1 (en) | 1999-07-09 | 2002-05-02 | Bourjois | Article for applying a topical composition and method for preparing same |
FR2796528B1 (en) | 1999-07-21 | 2001-09-21 | Oreal | DEVICE FOR CONDITIONING AND APPLYING A PRODUCT TO EYELASHES OR EYEBROWS |
AU4929600A (en) * | 1999-07-21 | 2001-02-05 | L'oreal | Device for applying a product on keratinous fibres |
DE19939326A1 (en) | 1999-08-19 | 2001-02-22 | Basf Ag | Aqueous cosmetic composition, e.g. nail varnish or hair setting lotion, contains an emulsion polymer with a glass transition point above room temperature and a minimum film-forming temperature below this |
FR2798061A1 (en) | 1999-09-07 | 2001-03-09 | Oreal | COSMETIC COMPOSITION COMPRISING PARTICLE DISPERSIONS OF POLYMERS IN A LIQUID FATTY PHASE |
US7101928B1 (en) | 1999-09-17 | 2006-09-05 | Landec Corporation | Polymeric thickeners for oil-containing compositions |
US6124490A (en) | 1999-10-26 | 2000-09-26 | Mona Industries, Inc. | Zwitterionic siloxane polymers and ionically cross-linked polymers formed therefrom |
US6309629B1 (en) * | 1999-12-14 | 2001-10-30 | Avon Products, Inc. | Wear resistant cosmetic compositions |
EP1112735A1 (en) * | 1999-12-20 | 2001-07-04 | Avon Products, Inc. | Cosmetic composition applied to the eyelashes |
FR2803743B1 (en) | 2000-01-14 | 2005-04-15 | Atofina | COSMETIC COMPOSITIONS CONTAINING AQUEOUS DISPERSIONS OF POLYMERS, FILMOGENES IN THE ABSENCE OF ORGANIC SOLVENT |
JP4768103B2 (en) * | 2000-06-06 | 2011-09-07 | 日東電工株式会社 | Adhesive composition, its adhesive sheet and method for producing them |
FR2810237B1 (en) | 2000-06-15 | 2002-07-26 | Oreal | FILM-FORMING COSMETIC COMPOSITION |
US6423304B1 (en) | 2000-06-15 | 2002-07-23 | Cognis Corporation | Dimerized fatty acid based polyamides useful for clear candle and gel applications |
US6410005B1 (en) * | 2000-06-15 | 2002-06-25 | Pmd Holdings Corp. | Branched/block copolymers for treatment of keratinous substrates |
FR2811546B1 (en) | 2000-07-13 | 2003-09-26 | Oreal | LONG-LASTING MAKEUP KIT AND METHOD |
US6518364B2 (en) * | 2000-09-28 | 2003-02-11 | Symyx Technologies, Inc. | Emulsion living-type free radical polymerization, methods and products of same |
AU9303801A (en) | 2000-10-25 | 2002-05-06 | 3M Innovative Properties Co | Acrylic-based copolymer compositions for cosmetic and personal care |
US20020076390A1 (en) | 2000-10-25 | 2002-06-20 | 3M Innovative Properties Company | Acrylic-based copolymer compositions for cosmetic and personal care |
FR2815847B1 (en) | 2000-10-27 | 2002-12-13 | Oreal | COSMETIC COMPOSITION COMPRISING FIBERS AND WAX |
DE10059826A1 (en) | 2000-12-01 | 2002-06-13 | Clariant Gmbh | Cosmetic, pharmaceutical and dermatological agents |
DE10059821A1 (en) | 2000-12-01 | 2002-06-13 | Clariant Gmbh | Surfactant-free cosmetic, dermatological and pharmaceutical agents |
DE10059824A1 (en) * | 2000-12-01 | 2002-06-13 | Clariant Gmbh | Electrolyte-containing cosmetic, pharmaceutical and dermatological agents |
DE10059818A1 (en) * | 2000-12-01 | 2002-06-13 | Clariant Gmbh | Decorative cosmetic and dermatological means |
DE10059830A1 (en) * | 2000-12-01 | 2002-06-13 | Clariant Gmbh | Cationically modified comb polymers based on acryloyldimethyltauric acid |
DE10059831A1 (en) * | 2000-12-01 | 2002-06-13 | Clariant Gmbh | Silicon-modified comb polymers based on acryloyldimethyltauric acid |
DE10059819A1 (en) * | 2000-12-01 | 2002-06-13 | Clariant Gmbh | Surfactant-containing cosmetic, dermatological and pharmaceutical agents |
JP2002327102A (en) | 2000-12-01 | 2002-11-15 | Clariant Gmbh | Composition containing copolymer based on acryloyldimethyltaurine acid and synergistic additive |
DE10059832A1 (en) * | 2000-12-01 | 2002-06-13 | Clariant Gmbh | Grafted copolymers based on acryloyldimethyltauric acid |
DE10059827A1 (en) | 2000-12-01 | 2002-06-20 | Clariant Gmbh | Cosmetic and dermatological hair treatment products |
DE10059823A1 (en) * | 2000-12-01 | 2002-06-13 | Clariant Gmbh | Deodorants and antiperspirants |
DE10059828A1 (en) | 2000-12-01 | 2002-06-13 | Clariant Gmbh | Comb-shaped copolymers based on acryloyldimethyltauric acid |
DE10059822A1 (en) * | 2000-12-01 | 2002-06-13 | Clariant Gmbh | Acid cosmetic, pharmaceutical and dermatological agents |
DE10059829A1 (en) | 2000-12-01 | 2002-06-13 | Clariant Gmbh | Grafted comb polymers based on acryloyldimethyltauric acid |
DE10059833A1 (en) | 2000-12-01 | 2002-06-13 | Clariant Gmbh | Fluorine-modified comb polymers based on acryloyldimethylauric acid |
DE10059825A1 (en) * | 2000-12-01 | 2002-06-13 | Clariant Gmbh | Use of comb-shaped copolymers based on acryloyldimethyltauric acid in cosmetic, pharmaceutical and dermatological agents |
JP2002201244A (en) | 2000-12-28 | 2002-07-19 | Nippon Shokubai Co Ltd | Acrylic block copolymer, composition for vibration- damping material, and production method for acrylic block copolymer |
US20020159960A1 (en) | 2001-02-27 | 2002-10-31 | Scancarella Neil D. | Method for improving the properties of transfer resistant lip compositions and related compositions and articles |
US20030039621A1 (en) * | 2001-04-10 | 2003-02-27 | L'oreal | Two-coat make-up product, its use and a kit containing the make-up product |
FR2823101B1 (en) | 2001-04-10 | 2004-02-06 | Oreal | TWO-LAYER MAKEUP PRODUCT, USES THEREOF AND MAKEUP KIT CONTAINING THIS PRODUCT |
FR2824267B1 (en) * | 2001-05-04 | 2008-06-27 | Oreal | COSMETIC COMPOSITION FILMOGENE |
JP4666442B2 (en) | 2001-07-27 | 2011-04-06 | 株式会社吉野工業所 | Shock absorbing container |
US20030024074A1 (en) * | 2001-08-01 | 2003-02-06 | Hartman Paul H. | Biconcave connector for tubular assemblies and tool handles |
JP3971381B2 (en) | 2001-08-21 | 2007-09-05 | ロレアル ユーエスエイ, インク. | Virtual hinge |
CN1607934A (en) * | 2001-09-13 | 2005-04-20 | 三菱化学株式会社 | Cosmetic resin composition and cosmetic |
JP2003286142A (en) | 2002-03-29 | 2003-10-07 | Mitsubishi Chemicals Corp | Polymer composition for hair cosmetic and the resulting hair cosmetic |
JP4039829B2 (en) * | 2001-09-13 | 2008-01-30 | 三菱化学株式会社 | Resin composition for cosmetics and cosmetics using the same |
FR2831430B1 (en) | 2001-10-26 | 2004-02-06 | Oreal | COSMETIC AND / OR CARE COMPOSITION CONTAINING A NON-CROSSLINKED POLYESTER-SILOXANE |
EP1448646A2 (en) | 2001-11-29 | 2004-08-25 | L'oreal | Adhesive block ethylene copolymers, cosmetic compositions containing same, and use thereof in cosmetics |
FR2834458A1 (en) | 2002-01-08 | 2003-07-11 | Oreal | Composition especially useful as nail varnish comprises two film-forming polymers with high and low glass transition temperatures dispersed as solid particles in an aqueous medium |
US20030185774A1 (en) | 2002-04-02 | 2003-10-02 | Dobbs Suzanne Winegar | Cosmetic coating composition comprising carboxyalkyl cellulose ester |
FR2840205B1 (en) | 2002-05-31 | 2005-08-05 | Oreal | SHAMPOO CONTAINING AT LEAST ONE AMPHIPHILIC SEQUENCE COPOLYMER AND AT LEAST ONE CATIONIC OR AMPHOTERIC POLYMER |
FR2840209B1 (en) * | 2002-05-31 | 2005-09-16 | Oreal | AQUEOUS CAPILLARY COMPOSITION THREADED BY LINEAR COPOLYMER AMPHIPHILE SEQUENCE |
US7176170B2 (en) | 2002-05-31 | 2007-02-13 | L'oreal | Shampoo comprising at least one silicone and at least one anionic or nonionic, amphiphilic linear block copolymer |
FR2840206B1 (en) | 2002-05-31 | 2005-08-05 | Oreal | SHAMPOO CONTAINING AT LEAST ONE SILICONE AND AT LEAST ONE LINEAR COPOLYMER AMPHIPHILE, ANIONIC OR NON-IONIC |
FR2842417B1 (en) | 2002-07-19 | 2005-01-21 | Oreal | COSMETIC COMPOSITION |
US7008629B2 (en) * | 2002-07-22 | 2006-03-07 | L'ORéAL S.A. | Compositions comprising at least one heteropolymer and fibers, and methods of using the same |
DE60314963T2 (en) | 2002-09-06 | 2008-04-10 | L'oreal | A method of decorative treatment of the eyelashes with a coating agent containing a sticky wax |
EP1534218B1 (en) | 2002-09-06 | 2009-12-16 | L'oreal | Make-up composition for keratin fibres such as eyelashes |
US20060099231A1 (en) | 2002-09-06 | 2006-05-11 | De La Poterie Valerie | Make-up composition for keratin fibres such as eyelashes |
US7923002B2 (en) | 2002-09-06 | 2011-04-12 | L'oreal S.A. | Composition for coating keratin fibres comprising a tacky wax |
GB2392910A (en) | 2002-09-10 | 2004-03-17 | Bayer Ag | 2-Oxopyrimidine derivatives and their use as human leukocyte elastase inhibitors |
EP1546113B1 (en) | 2002-09-10 | 2013-05-01 | Bayer Intellectual Property GmbH | Pyrimidinone derivatives as therapeutic agents against acute and chronic inflammatory, ischaemic and remodelling processes |
US20060128578A9 (en) | 2002-09-20 | 2006-06-15 | Nathalie Jager Lezer | Cosmetic composition comprising rigid fibres and at least one compound chosen from film-forming polymers and waxes |
FR2844709A1 (en) | 2002-09-20 | 2004-03-26 | Oreal | Plastic, thixotropic composition, preferably for make-up or care of keratin fibers, especially mascara, containing film-forming polymer or wax and rigid, rectilinear fibers to ensure homogeneous deposition |
US6905696B2 (en) | 2003-01-06 | 2005-06-14 | Color Access, Inc. | Alignment of enhancers in cosmetic compositions |
FR2860156B1 (en) | 2003-09-26 | 2007-11-02 | Oreal | COSMETIC COMPOSITION COMPRISING A TENSOR AGENT AND A PARTICULAR SEQUENCE ETHYLENIC POLYMER |
FR2860142B1 (en) | 2003-09-26 | 2007-08-17 | Oreal | COSMETIC BILOUCHE PRODUCT, USES THEREOF, AND MAKE-UP KIT CONTAINING THE SAME |
FR2864894A1 (en) * | 2004-01-13 | 2005-07-15 | Oreal | Easily applied keratin fiber coating composition, especially mascara, containing film-forming linear sequenced ethylenic polymer and fibers |
FR2864896B1 (en) | 2004-01-13 | 2006-03-31 | Oreal | KERATIN FIBER COATING COMPOSITION COMPRISING A SEQUENCE POLYMER AND A SEMI-CRYSTALLINE POLYMER |
US20050220731A1 (en) * | 2004-03-23 | 2005-10-06 | Philippe Ilekti | Nail varnish composition comprising at least one polymer and at least one plasticizer |
DE102004014806B4 (en) * | 2004-03-24 | 2006-09-14 | Daimlerchrysler Ag | Rapid technology component |
FR2871057B1 (en) | 2004-06-08 | 2006-07-28 | Oreal | COSMETIC COMPOSITION CONTAINING AN ESTER AND A FILMOGENIC AGENT |
US20050287103A1 (en) | 2004-06-08 | 2005-12-29 | Vanina Filippi | Cosmetic composition comprising at least one ester and at least one film-forming polymer |
FR2876011B1 (en) | 2004-10-05 | 2006-12-29 | Oreal | METHOD FOR MAKE-UP A SUPPORT AND KIT FOR IMPLEMENTING SAID METHOD |
JP2006151867A (en) | 2004-11-29 | 2006-06-15 | Rohto Pharmaceut Co Ltd | Solid lip gloss |
FR2880268B1 (en) | 2005-01-05 | 2008-10-24 | Oreal | BRILLIANT, NON-TRANSFERRING COMPOSITION COMPRISING TWO POLYMERIC SEQUENCES |
US20070134181A1 (en) | 2005-12-08 | 2007-06-14 | L'oreal | Cosmetic composition comprising an ester of dimerdilinoleic acid and of polyol(s) and a silicone surfactant |
FR2904320B1 (en) * | 2006-07-27 | 2008-09-05 | Oreal | POLYMER SEQUENCES, AND PROCESS FOR THEIR PREPARATION |
FR2904218B1 (en) | 2006-07-27 | 2012-10-05 | Oreal | COSMETIC COMPOSITION COMPRISING A COPOLYMER, A NONVOLATILE OIL AND A BRILLIANT OIL. |
CN101951992B (en) | 2007-12-05 | 2015-06-10 | 欧莱雅公司 | Cosmetic method using a composition comprising a siloxane resin and a mineral filler |
ES2645387T3 (en) | 2009-06-01 | 2017-12-05 | L'oréal | Cosmetic composition comprising a sequenced polymer and a non-volatile ester oil |
GB0922457D0 (en) | 2009-12-23 | 2010-02-03 | Parry Mark | GPS enabled software that appraises surfing performance on a mobile device |
US9192561B2 (en) | 2010-05-14 | 2015-11-24 | L'oreal | Compositions containing hyperbranched polyol and acrylic film former |
US8586013B2 (en) | 2010-12-30 | 2013-11-19 | L'oreal | Comfortable, long-wearing, transfer-resistant colored cosmetic compositions having a non-tacky feel |
US10076487B2 (en) | 2010-12-30 | 2018-09-18 | L'oreal | Comfortable, long-wearing, transfer-resistant colored cosmetic compositions |
-
2003
- 2003-09-26 BR BR0303890A patent/BR0303890A/en not_active IP Right Cessation
- 2003-09-26 AT AT03776945T patent/ATE488222T1/en not_active IP Right Cessation
- 2003-09-26 EP EP20030292383 patent/EP1421928A3/en not_active Ceased
- 2003-09-26 AU AU2003290143A patent/AU2003290143A1/en not_active Abandoned
- 2003-09-26 US US10/529,266 patent/US20060134051A1/en not_active Abandoned
- 2003-09-26 EP EP03778378A patent/EP1545443A2/en not_active Withdrawn
- 2003-09-26 DE DE60335007T patent/DE60335007D1/en not_active Expired - Lifetime
- 2003-09-26 WO PCT/FR2003/002840 patent/WO2004028492A2/en not_active Application Discontinuation
- 2003-09-26 WO PCT/FR2003/002842 patent/WO2004028488A2/en active Application Filing
- 2003-09-26 AU AU2003283477A patent/AU2003283477A1/en not_active Abandoned
- 2003-09-26 AU AU2003299071A patent/AU2003299071A1/en not_active Abandoned
- 2003-09-26 AU AU2003299069A patent/AU2003299069A1/en not_active Abandoned
- 2003-09-26 EP EP20030780204 patent/EP1545439B1/en not_active Expired - Lifetime
- 2003-09-26 AT AT03798230T patent/ATE488221T1/en not_active IP Right Cessation
- 2003-09-26 BR BR0314489A patent/BR0314489A/en not_active IP Right Cessation
- 2003-09-26 AU AU2003283478A patent/AU2003283478A1/en not_active Abandoned
- 2003-09-26 EP EP20030798230 patent/EP1545436B1/en not_active Expired - Lifetime
- 2003-09-26 AU AU2003299072A patent/AU2003299072A1/en not_active Abandoned
- 2003-09-26 DE DE60335996T patent/DE60335996D1/en not_active Expired - Lifetime
- 2003-09-26 US US10/529,265 patent/US9017704B2/en active Active
- 2003-09-26 US US10/528,835 patent/US8992903B2/en active Active
- 2003-09-26 US US10/529,218 patent/US20060115444A1/en not_active Abandoned
- 2003-09-26 EP EP03775450A patent/EP1545450A2/en not_active Withdrawn
- 2003-09-26 WO PCT/FR2003/002841 patent/WO2004028493A2/en active Application Filing
- 2003-09-26 JP JP2005501935A patent/JP3981132B2/en not_active Expired - Lifetime
- 2003-09-26 US US10/528,699 patent/US20060134032A1/en not_active Abandoned
- 2003-09-26 WO PCT/FR2003/002843 patent/WO2004028489A2/en active Application Filing
- 2003-09-26 EP EP20030798228 patent/EP1565148B1/en not_active Expired - Lifetime
- 2003-09-26 WO PCT/FR2003/002845 patent/WO2004028491A2/en active Application Filing
- 2003-09-26 US US10/529,267 patent/US20060099164A1/en not_active Abandoned
- 2003-09-26 AU AU2003286204A patent/AU2003286204A1/en not_active Abandoned
- 2003-09-26 DE DE60334709T patent/DE60334709D1/en not_active Expired - Lifetime
- 2003-09-26 AU AU2003285389A patent/AU2003285389A1/en not_active Abandoned
- 2003-09-26 JP JP2003336450A patent/JP2004269497A/en active Pending
- 2003-09-26 WO PCT/FR2003/002848 patent/WO2004028486A2/en active Application Filing
- 2003-09-26 DE DE60334921T patent/DE60334921D1/en not_active Expired - Lifetime
- 2003-09-26 JP JP2005501929A patent/JP3981128B2/en not_active Expired - Fee Related
- 2003-09-26 WO PCT/FR2003/002849 patent/WO2004028487A2/en active Application Filing
- 2003-09-26 EP EP20030776945 patent/EP1545438B1/en not_active Expired - Lifetime
- 2003-09-26 EP EP20030782505 patent/EP1545440B1/en not_active Expired - Lifetime
- 2003-09-26 JP JP2005501930A patent/JP3981129B2/en not_active Expired - Fee Related
- 2003-09-26 EP EP20030798229 patent/EP1545441B1/en not_active Expired - Lifetime
- 2003-09-26 AT AT03780204T patent/ATE485809T1/en not_active IP Right Cessation
- 2003-09-26 JP JP2005501928A patent/JP3984268B2/en not_active Expired - Fee Related
- 2003-09-26 AT AT03798229T patent/ATE497756T1/en not_active IP Right Cessation
- 2003-09-26 JP JP2005501936A patent/JP3981133B2/en not_active Expired - Lifetime
- 2003-09-26 DE DE60335009T patent/DE60335009D1/en not_active Expired - Lifetime
- 2003-09-26 AT AT03798231T patent/ATE487468T1/en not_active IP Right Cessation
- 2003-09-26 DE DE60335008T patent/DE60335008D1/en not_active Expired - Lifetime
- 2003-09-26 EP EP20030798231 patent/EP1545442B1/en not_active Expired - Lifetime
- 2003-09-26 US US10/529,318 patent/US7875265B2/en not_active Expired - Fee Related
- 2003-09-26 JP JP2005501934A patent/JP3981131B2/en not_active Expired - Fee Related
- 2003-09-26 AU AU2003288305A patent/AU2003288305A1/en not_active Abandoned
- 2003-09-26 US US10/529,264 patent/US20060147403A1/en not_active Abandoned
- 2003-09-26 US US10/670,388 patent/US20040120906A1/en not_active Abandoned
- 2003-09-26 DE DE60336577T patent/DE60336577D1/en not_active Expired - Lifetime
- 2003-09-26 US US10/528,698 patent/US20060127334A1/en not_active Abandoned
- 2003-09-26 AT AT03782505T patent/ATE488276T1/en not_active IP Right Cessation
- 2003-09-26 AU AU2003299070A patent/AU2003299070A1/en not_active Abandoned
- 2003-09-26 JP JP2005501932A patent/JP3981130B2/en not_active Expired - Fee Related
- 2003-09-26 WO PCT/FR2003/002846 patent/WO2004028494A2/en not_active Application Discontinuation
- 2003-09-26 WO PCT/FR2003/002847 patent/WO2004028485A2/en active Application Filing
- 2003-09-26 WO PCT/FR2003/002844 patent/WO2004028490A2/en not_active Application Discontinuation
- 2003-09-26 AT AT03798228T patent/ATE503457T1/en not_active IP Right Cessation
Patent Citations (100)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2047398A (en) * | 1930-06-26 | 1936-07-14 | Ig Farbenindustrie Ag | Artificial resins and process of making them |
US2528378A (en) * | 1947-09-20 | 1950-10-31 | John J Mccabe Jr | Metal salts of substituted quaternary hydroxy cycloimidinic acid metal alcoholates and process for preparation of same |
US2723248A (en) * | 1954-10-01 | 1955-11-08 | Gen Aniline & Film Corp | Film-forming compositions |
US2781354A (en) * | 1956-03-26 | 1957-02-12 | John J Mccabe Jr | Imidazoline derivatives and process |
US3716633A (en) * | 1966-08-03 | 1973-02-13 | I Oreal Sa | Vinyl acetate-crotonic acid-unsaturated ester or ether polymers in hair lacquers and setting lotions |
US3910862A (en) * | 1970-01-30 | 1975-10-07 | Gaf Corp | Copolymers of vinyl pyrrolidone containing quarternary ammonium groups |
US3673160A (en) * | 1970-02-12 | 1972-06-27 | Rhodiaceta | Process for producing brilliant sulfonated polyamide-imide fibers and such fibers so produced |
US4032628A (en) * | 1970-04-07 | 1977-06-28 | Societe Anonyme Dite: L'oreal | Cosmetic emulsion compositions including black polymer emulsifiers |
US3836537A (en) * | 1970-10-07 | 1974-09-17 | Minnesota Mining & Mfg | Zwitterionic polymer hairsetting compositions and method of using same |
US3802841A (en) * | 1971-06-14 | 1974-04-09 | Rhone Poulenc Textile | Nitro aromatic hydrocarbon,amino nitro aromatic & nitro aromatic phosphine oxides on aromatic polyamide-imide as light fading inhibitors for dyes thereon |
US3990459A (en) * | 1972-06-20 | 1976-11-09 | Societe Anonyme Dite: L'oreal | Cationic graft and cross-linked copolymers in wavesetting lotions |
US3946749A (en) * | 1972-06-20 | 1976-03-30 | L'oreal | Hair cosmetic compositions based on grafted and crosslinked copolymers |
US3937811A (en) * | 1973-06-08 | 1976-02-10 | Societe Anonyme Dite: L'oreal | Fatty compositions for use in cosmetic makeup compositions and said cosmetic makeup compositions |
US3966404A (en) * | 1974-04-01 | 1976-06-29 | L'oreal | Hair laquer or hair setting composition containing a terpolymer |
US3966403A (en) * | 1974-04-01 | 1976-06-29 | L'oreal | Hair lacquer or hair setting composition containing a tetrapolymer |
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US4030512A (en) * | 1974-12-30 | 1977-06-21 | Societe Anonyme Dite: L'oreal | Hair lacquer or setting lotion containing bi- or tri-sequenced copolymer |
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US4296053A (en) * | 1979-05-24 | 1981-10-20 | Brown Group, Inc. | Method of making foamed plastisol insoles for shoes |
US5110582A (en) * | 1981-03-25 | 1992-05-05 | Basf Aktiengesellschaft | Hair-setting preparation |
US4459249A (en) * | 1982-01-22 | 1984-07-10 | Inoue Mtp Kabushiki Kaisha | Method of manufacturing a foamed protective and decorative molding for an automobile |
US4524037A (en) * | 1982-08-16 | 1985-06-18 | Michel Marc | Method and apparatus for forming a flexible thermoplastic resin foam article using an RF field |
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US4824617A (en) * | 1986-07-30 | 1989-04-25 | Inoue Mtp Kabushiki Kaisha | Method for manufacturing plastic foam |
US5266321A (en) * | 1988-03-31 | 1993-11-30 | Kobayashi Kose Co., Ltd. | Oily make-up cosmetic comprising oil base and silicone gel composition |
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US6372876B1 (en) * | 1992-07-29 | 2002-04-16 | Basf Aktiengesellschaft | Use of polyurethanes which are soluble or dispersible in water as aids in cosmetic and pharmaceutical compositions, and polyurethanes which contain polylactic acid polyols as copolymerized units |
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US20030191271A1 (en) * | 1993-08-04 | 2003-10-09 | Jean Mondet | New polyester polyurethanes, process for preparaing them, pseudolatices produced from the said polyester polyurethanes and their use in cosmetic compositions |
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US5538717A (en) * | 1993-10-15 | 1996-07-23 | L'oreal | Aqueous nail polish containing as film-forming substance particles of polyester-polyurethane which are anionic in dispersion |
US5843407A (en) * | 1993-10-18 | 1998-12-01 | The Procter & Gamble Company | Non-sweating lipsticks |
US6059473A (en) * | 1994-07-12 | 2000-05-09 | L'oreal | Applicator for applying a liquid cosmetic product and make-up assembly provided with such an applicator |
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US6027739A (en) * | 1995-05-15 | 2000-02-22 | Lip Ink International | Smear-resistant cosmetic |
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US6074654A (en) * | 1995-11-07 | 2000-06-13 | The Procter & Gamble Company | Transfer resistant cosmetic compositions |
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US6228967B1 (en) * | 1996-05-22 | 2001-05-08 | Mona Industries, Inc. | Organosilicone having a carboxyl functional group thereon |
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US6299807B1 (en) * | 1996-11-01 | 2001-10-09 | Honda Giken Kogyo Kabushiki Kaisha | Method for producing molded article |
US6267951B1 (en) * | 1997-03-26 | 2001-07-31 | Avon Products, Inc. | Cosmetic composition for the nails and hair |
US6303105B1 (en) * | 1997-03-26 | 2001-10-16 | Avon Products, Inc. | Cosmetic composition for imparting wear resistance and shine |
US6083516A (en) * | 1997-03-26 | 2000-07-04 | Avon Products, Inc. | Wear resistant cosmetics |
US6386781B1 (en) * | 1997-04-15 | 2002-05-14 | L'oreal | Unit for packaging and applying a liquid product |
US6106820A (en) * | 1997-05-12 | 2000-08-22 | Procter & Gamble Company | Cosmetic compositions |
US6153206A (en) * | 1997-08-27 | 2000-11-28 | Revlon Consumer Products Corporation | Cosmetic compositions |
US6238679B1 (en) * | 1998-03-09 | 2001-05-29 | L'oreal S.A. | Film-forming composition comprising a polyurethane in aqueous dispersion and a plasticizer |
US6225390B1 (en) * | 1998-05-08 | 2001-05-01 | Shell Oil Company | Oil gel formulations containing polystyrene-polydimethylsiloxane or polyethylene-polydimethylsiloxane block copolymers dissolved in siloxane monomers |
US20020055562A1 (en) * | 1998-10-29 | 2002-05-09 | Butuc S. Gina | Gel compositions |
US6268466B1 (en) * | 1999-01-04 | 2001-07-31 | Arizona Chemical Company | Tertiary amide terminated polyamides and uses thereof |
US20020035237A1 (en) * | 1999-01-04 | 2002-03-21 | Lawson Nelson E. | Structured composition containing tertiary amide-terminated polyamide for personal care products |
US6484731B1 (en) * | 1999-03-16 | 2002-11-26 | L'oreal | Single-piece articulated assembly |
US6692733B1 (en) * | 1999-04-06 | 2004-02-17 | L'oreal | Composition comprising polymers having a star structure, the polymers, and their use |
US6552146B1 (en) * | 1999-04-06 | 2003-04-22 | L'oreal S.A. | Composition comprising polymers having a star structure, the polymers, and their use |
US6960339B1 (en) * | 1999-07-15 | 2005-11-01 | L'oreal S.A. | Compositions structured with at least one polymer and methods of using the same |
US6581610B1 (en) * | 1999-07-21 | 2003-06-24 | L'oreal S.A. | Applicator, applicator system, and method for applying a product to the eyelashes |
US6174968B1 (en) * | 1999-08-24 | 2001-01-16 | Shell Oil Company | Oil gel formulations containing polysiloxane block copolymers dissolved in hydrogenated silicone oils |
US6843611B2 (en) * | 2000-03-16 | 2005-01-18 | L'oreal | Device for packaging and applying a cosmetic or care product |
US20020015611A1 (en) * | 2000-03-16 | 2002-02-07 | Gilles Blondeel | Device for packaging and applying a cosmetic or care product |
US20020018759A1 (en) * | 2000-05-04 | 2002-02-14 | Pagano Frank Charles | Nail enamel compositions, related methods, and a two component kit for painting the nails |
US20030113285A1 (en) * | 2000-05-08 | 2003-06-19 | Helmut Meffert | Polyurethane and the use thereof for modifying rheological properties |
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